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study of factors influencing the quality and yield of biodiesel

1. J UNIVERSITY OF G VLE FACULTY OF ENGINEERING AND SUSTAINABLE DEVELOPMENT STUDY OF FACTORS INFLUENCING THE QUALITY AND YIELD OF BIODIESEL PRODUCED BY TRANSESTERIFICATION OF VEGETABLE OILS Zaloa res Gondra June 2010 Master s Thesis n Energy Systems Master s Programme in Energy Systems Examiner Jan Akander Supervisor Peter Norberg PREFACE This paper is a final thesis for the Energy Systems Master Programme in the University of G vle It was carried out from March to June 2010 in the Faculty of Engineering and Sustainable Development which belongs to the university This thesis could not have been completed without the help and support of many people some of them are mentioned below First of all would like to thank Peter Norberg the supervisor of this thesis His willingness to help me and his interest concerning the project were essential for the success of it really appreciate the time he devoted to it as well as all his attention and support He certainly is a great source of knowledge about many different topics and this was very valuable for me would also like to thank all the people working in the Faculty of Engineering and Sustainable Development for providing their help when needed it and for making my stay comfortable Furthermore would like to express my gratitude to The Dallas Group of America for the delivery of different products needed for the completion of the thesis
2. OR R C O OR Step 2 OR ROH R C O HOR R C O OR OR OR Step 3 ROH R C O RCOOR HOR OK Where R OH dighveeride R long chain alkyl group and RK short alkyl group Figure 1 3 The mechanism of the alkali catalysed transesterification 21 The catalyst is not the alkali itself but the product created by mixing the alkali with the alcohol which is an alkoxide group When this reaction takes place a small amount of water is generated which may cause problems due to soap formation during transesterification 21 On the other hand if the catalyst used is an acid the mechanism will be defined by it therefore it will be an acid mechanism and the trigger will be a hydron 14 R OH elyceride OH R carbon chain of fatty acid R alkvl group ol the alcohol Figure 1 4 Acid catalysed transesterification 10 In this case the first step is the attack of the hydron of the acid on the carbonyl carbon atom forming the tetrahedral intermediate In the second step the alcohol will react with the intermediate due to its negative charge The last step is the rearrangement step with the hydron of the catalyst being liberated again and the formation of the diglycerol and the ester 3 2 4 Reaction conditions Once the reaction is known the conditions in which it happens should be determined The parameters that will affect the reaction to a higher extent are temperature amount of alcohol
3. 16 Furthermore the soap may lead to difficulties in the reaction and separation of the products The oils with higher amount of FFAs are usually waste vegetable oils that is oils that have been used for cooking purposes In the case of clean vegetable oils there should not be so high values of FFAs Other important motive to choose one type of oil over other is that the kind of biodiesel obtained depends highly on the oil that has been used to produce it Table 3 1 shows the kinematic viscosity of different oils and biodiesel obtained from different sources It can be appreciated that the oil from which is obtained will affect in difterent ways the kinematic viscosity of the product Kinematic viscosity of Kinematic viscosity of biodiesel Species oil centistokes at 40 C centistokes at 40 C Rapeseed 35 1 4 3 5 83 Soybean 32 9 4 08 Sunflower 32 6 4 9 Palm 39 6 4 42 Peanut 22 2 4 42 Corn 34 9 3 39 Canola 38 2 3 53 Cotton 18 2 4 07 Pumpkin 35 6 4 41 Table 3 1 Comparison between the kinematic viscosoties of vegetable oils and the biodiesel obtained from the oils 14 As in the case of the kinematic viscosity many other properties will vary depending on the source of vegetable oil For additional information examine Annex I 10 Apart from that there are some other important factors that must be taken into account For instance the possibility of obtaining a kind of vegetable oil depending on the geographical locat
4. However the water bubbling cleaning took almost five days Time is a powerful disadvantage of water bubbling when comparing it with other methods because dry cleaning takes usually less than one hour just 20 minutes for mixing and then some extra time for filtering the product On the other hand dry products are more expensive than water Therefore depending on different factors the most suitable method will have to be decided for every manufacturers conditions 52 100 0 75 0 Reduction soap al O O 25 0 0 Hi Magnesol 1 BE Magnesol 2 D Sol BE Aerogel 1 BE Aerogel 2 BE Water bubbling 3 steps BE Water bubbling 4 steps FD Magnesol 1 water bubbling Figure 6 11 Soap amount reduction with different products As mentioned the best result is obtained for the combination of Magnesol and water bubbling in that case 98 of the soap is removed Water bubbling with four steps and Magnesol are also good options but in the case of Magnesol two filtering papers were used so this results are not significative 6 5 Using the centrifuge Five different trials were performed with the centrifuge and only one of them had a satisfactory result It worked when using it to remove impurities from a raw sunflower oil Consequently its use is recommended when impurities from oils have to be removed but different systems should be used to remove water from both biodiesel and oil and to separate glycerol and biodiesel because it does
5. S P Singh Dipti Singh Biodiesel production through the use of different sources and characterization of oils and their esters as the substitute of diesel A review Renewable and Sustainable Energy Reviews 14 2010 200 216 11 Umer Rashid Farooq Anwar Production of biodiesel through optimized alkaline catalyzed transesterification of rapeseed oil Fuel 87 2008 265 273 12 H J Harwood Oleochemicals as a fuel Mechanical and economic feasibility JAOCS 61 1984 315 324 13 Y C Sharma B Singh S N Upadhyay Advancements in development and characterization of biodiesel A review Fuel 87 2008 2355 2373 14 Dennis Y C Leung Xuan Wu M K H Leung A review on biodiesel production using catalyzed transesterification Applied Energy 87 2010 1083 1095 15 Carter D Darby D Hall J Hunt P 2005 How to make biodiesel Milton Keynes Great Britain Lightening Source ISBN 0 9549171 0 3 16 Kemp W H 2006 Biodiesel Basics and Beyond A Comprehensive Guide to Production and Use for the Home and Farm Ontario Canada Aztext Press ISBN 0 9733233 3 7 17 Graham Towerton The use of ultrasonic reactors in a small scale continuous biodiesel process www customerchempack com 2007 18 Carlo Mazzocchia Giovanni Modica Akim Kaddouri Roberto Nannicini Fatty acid methyl esters synthesis from triglycerides over heterogeneous catalysts in presence of microwaves Comptes Rendus Chimie 7
6. it takes to produce diesel fuel it is a short period This means that it can be available in a short period of time Renewability Because of its origin which is oil produced from a crop it is renewable because this source can be restarted as many times as wanted 22 23 24 25 3 5 2 Disadvantages of biodiesel Even if biodiesel has several advantages its use also implies some disadvantages that should be mentioned 20 Agricultural feedstock is needed to produce biodiesel and at some times its availability might be constrained due to its necessity to produce food This may impose limits on the production of biodiesel The kinematic viscosity of biodiesel is higher than that of diesel fuel This affects fuel atomisation during injection and requires modified fuel injection systems Biodiesel has high oxygen content which when combusted produces higher NO levels than the produced by mineral diesel Oxidation of biodiesel happens more easily than oxidation of diesel so when it is stored for long periods some products that may be harmful to the vehicle components might be produced Biodiesel is hygroscopic it absorbs water easily Water content of biodiesel is limited by the standards Thus contact of biodiesel with sources of humidity should be avoided Partly due to its local and home production the biodiesel produced may not comply with European or US standards and it may cause corrosion fuel system block
7. should also mention my friends here in Gavle for their support and for sharing many great times with me Finally would like to thank my family particularly my parents because without their help none of this would have been possible No one mentioned no one forgotten Gavle June 2010 Zaloa Ares Gondra ABSTRACT Biofuels are a developing kind of fuel whose origin is biomass Among them many different kind of fuels can be found bioethanol biobutanol biodiesel vegetable oils biomethanol pyrolysis oils biogas and biohydrogen This thesis work is focused on the production of biodiesel which can be used in diesel engines as a substitute for mineral diesel Biodiesel is obtained from different kinds of oils both from vegetable and animal sources However vegetable oils are preferred because they tend to be liquid at room temperature The process to obtain biodiesel implies first a reaction between the oil and an alcohol using a catalyst and then a sedimentation where the biodiesel and the glycerol the two products that are obtained can be separated because of their difference in density After the separation raw biodiesel is obtained and a treatment with either water bubbling or dry cleaning products is needed to obtain the product which will be ready to use Many methods are available for the production of biodiesel most of them require heat for the transesterification reaction which converts the oil into biodiesel A
8. there are still a lot people interested in building new plants These companies are taking a good hard look at using dry washing Dugan says We have spoken to a lot of folks he says We have our systems specified into a lot of medium sized plants and we re talking to some of the larger plants I think that as soon as it makes sense to build up the industry capacity we will see an influx of busi ness that we can t even imagine That s really exciting for us W Jerry W Kram is a Biodiesel Magazine staff writer Reach him at jkram bbibiofuels com or 701 738 4962 SPECIALTY ADSORBENTS www dallasgrp com ANNEX VI CENTRIFUGE AND AC DRIVE 1 Centrifuge The centrifuge used in the different trials is a Basic Raw Power Centrifuge which is manufactured by WVO Designs lts main characteristics which can be found in http wvodesigns com are the following The Basic Raw Power Centrifuge runs at 3450rpm and produces over 1200Gs This entry level centrifuge is the lowest cost way to get out of filtering waste oil Consider the optional bolt on heater to increase flow rates to 15gph Single Pass Adjust flow rate to suit your feedstock and cleaning requirements Quiet Custom US Made Motor operates smooth and quiet it will be quieter than an A C Unit No Pressure High pressure pumps and fittings are expensive and leaks costly Direct Drive Rotor speed is unquestionable and you can t get a simpler d
9. type and amount of catalyst reaction time Further each of them will be discussed individually 3 2 4 1 Temperature Temperature values for the transesterification reaction vary depending on the literature source It is well known that higher temperatures speed up the reaction and shorten the reaction time Apart from that higher temperatures usually mean obtaining higher ester yields 11 However It should also be noted that if the reaction temperature is higher than the boiling point of the alcohol it will evaporate resulting in a lower yield 13 It is also an accepted fact that usually the optimum temperatures for the transesterification range between 50 and 60 C depending on the kind of oil to be processed 14 In the case of rapeseed oil the optimum temperature value for its methanolysis has been found to be 65 C 11 3 2 4 2 Reaction fime The reaction time clearly influences the outcome of the reaction since the conversion rate increases with the reaction time 21 If the reaction time is not long enough the ester yield will be low therefore part of the oil will be unreacted For the rapeseed oil when heat is used in the reaction the optimum reaction time is two hours 11 15 3 2 4 3 Methanol oil molar ratio This is one of the most important factors that can affect the ester yield It is related to the type of catalyst used depending on that the optimum value for the process can be obtained Higher molar ratios
10. 2004 601 605 19 N Saifuddin K H Chua Production of ethyl ester biodiesel from used frying oil optimization of transesterification process using microwave irradiation Malaysian Journal of Chemistry 6 2004 77 82 20 Man Kee Lam Keat Teong Lee Abdul Rahman Mohamed Homogeneous heterogeneous and enzymatic catalysis for transesterification of high free fatty acid oil waste cooking oil to biodiesel A review Biotechnology Advances 28 2010 500 518 57 21 Fangrui Maa Milford A Hannab Biodiesel production a review Bioresource Technology 70 1999 1 15 22 Robiah Yunus Ahmadun Fakhru l Razi Tian Lye Ooi Sunny E lyuke Joseph M Perez Lubrication properties of trimethylolpropane esters based on palm oil and palm kernel oils European Journal of Lipid Science and Technology 106 2004 52 60 23 Charles L Peterson Todd Hustrulid Carbon cycle for rapeseed oil biodiesel fuels Biomass and Bioenergy 14 1998 91 101 24 O M I Nwafor G Rice Performance of rapeseed methyl ester in diesel engine Renewable Energy 6 1995 335 342 25 Ayhan Demirbas Biofuels securing the planet s future energy needs Energy Conversion and Management 50 2009 2239 2249 26 Make Biodiesel Two stage acid base recipes http make biodiesel org index php option com_content amp view article amp id 76 amp ltemid 9 8 Access 2010 05 27 27 Make Biodiesel The 3 27 Conversion Test http make biod
11. 53 6 44 6 40 5 10 0 12 2 274 0 9048 0 23 Linseed 27 2 34 6 39 2 17 15 0 241 0 9236 0 22 Peanut 39 6 41 8 39 8 12 8 6 7 271 0 9026 0 24 Rapeseed 37 0 37 6 39 7 3 9 31 7 246 0 9115 0 30 Safflower 31 3 41 3 39 5 18 3 6 7 260 0 9144 0 25 Sesame 35 5 40 2 39 3 3 9 9 4 260 0 9133 0 24 Soya bean 32 6 37 9 39 6 3 9 12 2 254 0 9138 0 25 Sunflower 33 9 37 1 39 6 7 2 15 0 274 0 9161 0 27 Palm 39 6 42 0 31 0 267 0 9180 0 23 Babassu 30 3 38 0 20 0 150 0 9460 Diesel 3 06 50 43 8 16 76 0 855 Source S P Singh Dipti Singh Biodiesel production through the use of different sources and characterization of oils and their esters as the substitute of diesel A review Renewable and Sustainable Energy Reviews 14 2010 200 216 ANNEX Il BIODIESEL STANDARDS 1 European Standard for Biodiesel EN 14214 Property Ester content Density at 15 C Viscosity at 40 C Flash point Sulphur content Carbon residue on 10 distillation residue Cetane number Sulphated ash content Water content Total contamination Copper strip corrosion 3h at 50 C Oxidation stability 110 C Acid value lodine value Linolic acid methyl ester Fatty acid methyl esters gt 4 double bonds Methanol content Monoglyceride content Diglyceride content Triglyceride content Free glycerol Total glycerol Alkaline metals Na K Alkaline earth metals Ca Mg Testing method EN 14103 EN ISO 3675 EN ISO 12185 EN ISO 3104 ISO 3105
12. 6FAC RJ 12 Serial Comm Port eure O O 4 Interface See Warning External Fault N O Pressure RS 485 Sensors 2 GND T eo HA AJog on o 4 SG Pushbuttonsl E Communication Port 5 5V eats A Common signan A Optional ZIPLink RS485 ds Communication cable GS 485HD15 Relais CBL available for connection to the ee er DLO6 and D2 260 15 pin Analog voltage 2 10V 10mA ports See page 12 75 DAS Comm 0 1 OVDC max ZIRIN u Potentiometer COIN Blocks amp 3 5 KO Al AN Wiring Analog current l En 0 20 mA A 20mA T Circuit Protection Enclosures Tools Ak Factory default setting Pneumatics Factory default source of frequency command is via the keypad potentiometer Ne O Main circuit power terminals Control circuit terminal Shielded leads Poda WARNING Do not plug a modem or telephone into the GS1 RJ 12 Serial Comm Port or permanent damage may result in Terminals 2 and 5 should not be used as a power source for your communication connection Volume 13 www automationdirect com drives Drives Motors Motion el3 19 GS1 Specifications Dimensions 68 0 2 68 2 68 E 29 56 0 2 20 _ 9 Ne l EZ L3 E VO AITA D _ pesg V el G DO E STOP ENTER on A NI O 2 S N N 3 S CO ao Ni m I l S CO E i S N N Volume 13 el 3 20 l Drives Motors Motion 128 1 5 04 Unit mm in 1 800 633 0405
13. 7 1 Equipment 4 7 2 Reagents 4 7 3 Procedure 4 8 Soap test 23 25 29 24 24 24 25 28 28 28 28 28 28 28 29 29 29 30 30 30 30 30 31 31 31 31 31 4 8 1 Equipment 4 8 2 Reagents 4 8 3 Procedure 4 9 Using the centrifuge 4 9 1 Equipment 4 9 2 Reagents 4 9 3 Procedure 5 RESULTS 5 1 Titration 5 2 Biodiesel production 5 2 1 Influence of the catalyst 5 2 2 Influence of methanol 5 2 3 Influence of the temperature 5 2 4 Experiments with different kinds of oils 5 3 Soap titration 5 4 Cleaning biodiesel 5 5 Using the centrifuge 6 DISCUSSION 6 1 Titration 6 2 Biodiesel production 6 2 1 Reaction time 6 2 2 Influence of the catalyst 6 2 3 Influence of methanol 6 2 4 Influence of the temperature 6 2 5 Experiments with different kinds of oils 6 3 Soap titration 6 4 Cleaning biodiesel 3 3 32 32 32 32 33 35 35 35 35 38 40 41 41 42 43 45 45 45 45 45 48 49 5 52 52 6 5 Using the centrifuge 6 6 Methanol 7 CONCLUSION 8 REFERENCES ANNEX I PROPERTIES OF VEGETABLE OILS ANNEX Il BIODIESEL STANDARDS ANNEX Ill LABORATORY EQUIPMENT ANNEX IV AIR BUBBLING MACHINE ANNEX V DRY CLEANING PRODUCTS ANNEX VI CENTRIFUGE AND AC DRIVE 53 53 55 57 I INTRODUCTION 1 1 Background Energy is one of the big worries of the humanity nowadays In fact not energy itself but the sources of the energy There are several issues around this topic On the one hand there is the always recurrent en
14. C for two hours It was weighed both before and after the heating and no significative reduction of weight was noticed as shown in table 6 2 Vbiodieser ML Wbiodiesel 9 Before heating 305 264 4 After heating 315 262 5 Figure 6 2 Methanol removal To sum up in this case methanol was not taken into account because it is not important for the purpose of the thesis but when producing biodiesel in big batches its presence should be considered and a process to do so will probably be necessary 54 7 CONCLUSION First of all it can be stated that the purpose of the thesis was fulfilled a method for producing biodiesel at room temperature was developed and it seems to be valid since complete transesterification of the oil is achieved Moreover the procedure has been tried with different oils and catalysts and worked in all cases Nevertheless there are some limitations that may change the outcome if considered Firstly the fact that a detailed analysis of the biodiesel obtained could not be done because of the lack of a gas chromatography system Because of this simple analyses as the 3 27 test and soap titrations are the only proof of the validity of this method Another issue that deserves to be focused on is methanol lt has been disregarded during the experimental procedure because it is not a key question in this case but it is when producing biodiesel in big quantities Therefore it should be considered when producing bi
15. EN ISO 3679 EN ISO 20846 EN ISO 20884 EN ISO 10370 EN ISO 5165 ISO 3987 EN ISO 12937 EN 12662 EN ISO 2160 EN 14112 EN 14104 EN 14111 EN 14103 EN 14110 EN 14105 EN 14105 EN 14105 EN 14105 EN 14106 EN 14105 EN 14108 EN 14109 prEN 14538 Limits Min 96 5 860 3 5 120 51 6 0 Max 900 5 0 10 0 0 3 0 02 500 24 0 5 120 12 0 20 0 80 0 20 0 20 0 02 0 25 5 0 5 0 Unit m m kg m8 mm s C mg kg m m m m mg kg mg kg h mg KOH kg g iodine 100g m m m m m m m m m m m m m m m m mg kg mg kg Limits Property Testing method Unit Min Max Phosphorus content EN 14107 10 0 mg kg Source BASF Group 2 Specification for Biodiesel B100 ASTM D6751 08 Property ASTM Method Calcium amp Magnesium combined EN 14538 Flash Point closed cup D 93 Alcohol Control One of the following must be met 1 Methanol Content EN 14110 2 Flash Point D 93 Water amp Sediment D 2709 Kinematic Viscosity 40 C D 445 Sulphated ash D 874 Sulphur S 15 Grade D 5453 S 100 Grade D 5453 Copper Strip Corrosion D 130 Cetane D 613 Cloud Point D 2500 Carbon Residue 100 sample D 4530 Acid Number D 664 Free Glycerin D 6584 Total Glycerin D 6584 Phosphorus Content D 4951 Distillation TOOAET D 1160 Sodium Potassium combined EN 14538 Oxidation Stability EN 14112 Cold Soak Filtration
16. For use in temperatures below 12 C Annex to D6751 Annex to D6751 Limits 5 maximum 93 maximum 0 2 maximum 130 minimum 0 05 maximum 1 9 6 0 0 02 maximum 0 0015 max 15 0 05 max 500 No 3 maximum 47 minimum report 0 05 maximum 0 50 maximum 0 020 maximum 0 240 maximum 0 001 maximum 360 maximum 5 maximum 3 minimum 360 maximum 200 maximum Source the National Biodiesel Board Units ppm ug g IC volume eC volume mm2 s mass mass ppm mass ppm C mass mg KOH g mass mass mass C ppm hours seconds seconds ANNEX Ill LABORATORY EQUIPMENT In the table the pictures and names of all the laboratory equipment which was used during the project can be seen Weight balance 3 Magnetic stirrer 4 iid E w E Fe il RT ii CIN w L Kitasato flask 11 B chner funnel 12 QUALITATIVE a FILTER PAPER Filter paper 13 Vacuum pump 14 Sources 1 Wikipedia Emil Erlenmeyer http en wikipedia org wiki File Erlenmeyer_flask jpg Access 2010 06 16 2 Supplierlist Quartz crystals http www supplierlist com wholesale quartz_crystals 7032 htm Access 2010 06 16 3 PCE http www pce group europe com espanol product_info php info p5375_Balanza compacta PCE BSH 10000 html Access 2010 06 16 4 Direct Industry Stuart Equipment http www directindustry com prod stuart equipment laboratory hot pla
17. Inc products you buy process use or distribute and you are encouraged to advise anyone working with or exposed to such products of the information contained in the applicable data sheets THE DATA IN THIS DOCUMENT IS PROVIDED WITHOUT ANY REPRESENTATION OR WARRANTY EXPRESSED OR IMPLIED REGARDING ITS ACCURACY OR CORRECTNESS NO WARRANTY EITHER EXPRESSED OR IMPLIED OF MERCHANTABILITY OR FITNESS OR OF ANY NATURE IS MADE WITH RESPECT TO ANY PRODUCT REFERRED TO HEREIN THE DALLAS GROUP OF AMERICA INC DOES NOT ASSUME RESPONSIBILITY AND EXPRESSLY DISCLAIMS LIABILITY FOR LOSS DAMAGE OR EXPENSE ARISING OUT OF OR IN ANY WAY CONNECTED WITH THE HANDLING STORAGE USE OR DISPOSAL OF THE PRODUCTS REFERRED TO HEREIN The data contained herein is being supplied for the limited purpose of complying with the OSHA Right to Know Regulation 29 CFR 1910 1200 The submission of this MSDS may be required by law but this is not an assertion that this substance is hazardous when used in accordance with proper safety practices and normal handling procedures FOR MORE INFORMATION CALL 812 283 6675 Revised 10 27 2009 ASTM D6751 EN 14214 SPECIFICATIONS Parameter Soap mg kg None Free Glycerin 0 020 max Total Glycerin 0 240 max Flash Point C 130 min Metals Na K mg kg 5 0 max Metals II Mg Ca mg kg 5 0 max Oxidation Stability 110 C hours 3 0 min Water mg kg 500 max Sulfated Ash mass 0 020 max Methanol Content None 1 812 283 667
18. Pressure N A Viscosity N A Boiling Point N A Vapor Density N A Volatile N A Evaporation Rate N A Ignition Temperature N A N A Not applicable 10 STABILITY AND REACTIVITY 10 1 Conditions to avoid None in designated use 10 2 Materials to avoid None in designated use 10 3 Hazardous Decomposition Products None the substance is stable Note In sufficient quantity a filter cake composed of a flammable organic liquid absorbed on synthetic magnesium silicate or other filter materials such as diatomaceous earth Perlite or natural clays may be self heating or possibly pyrophoric o A self heating material is a material that when in contact with air and without an energy supply is liable to self heat A material of this type which exhibits spontaneous ignition or if the temperature of the sample exceeds 200 C 392 F during the 24 hour test period when tested in accordance with UN Manual of Tests and Criteria is classed as a Division 4 2 material o Apyrophoric material is a liquid or solid that even in small quantities and without an external ignition source can ignite within five 5 minutes after coming in contact with air when tested according to the UN Manual of Tests and Criteria 11 TOXICOLOGICAL INFORMATION This product does not contain any ingredient designated by IARC NTP ACGIH or OSHA as probable or suspected human carcinogens Studies conducted in 1989 at Hil
19. Sulphur D 5453 0 05 max wt Sulphur D 2622 129 0 05 max wt Copper strip corrosion D 130 No 3 max No 3 max Cetane number D 613 40 min 47 min Aromaticity D 1319 35 max vol 17 Fuel Property Test method ASTM D975 Diesel ASTM D6715 Biodiesel Carbon residue D 4530 0 05 max mass Carbon residue D 524 0 35 max mass Distillation temp 90 volume D 1160 555 K min 611 K max recycle Table 3 4 ASTM standards of biodiesel and petrodiesel fuels 3 More information about biodiesel standards can be found in the Annex Il 3 5 Advantages and disadvantages of biodiesel As it has been mentioned above biodiesel can be used as a substitute for mineral diesel When using it several different advantages and disadvantages can be found In the lines below those will be explained in detail 3 5 1 Advantages of biodiesel The advantages of using biodiesel can be divided into three categories 3 5 1 1 Economic impacts Sustainability Biodiesel promotes sustainability because it is a renewable fuel with no carbon dioxide emissions and that avoids the use of fossil fuels Fuel diversity It means more competition and also more options for the consumer that way the quality of the products is enhanced and the prices are lower Increased number of rural manufacturing jobs In order to grow the seeds produce the oil and then the biodiesel several workers are needed Usually this will happen in rural areas meaning that more jobs will
20. a suitable solvent it is done by diluting the vegetable oil with mineral diesel to run the engine b Emulsification also called microemulsion it can be defined as a colloidal equilibrium dispersion of optically isotropic fluid microstructure with dimensions generally into 1 150 range formed spontaneously from two normally immiscible liquids and one and more ionic or more ionic amphiphiles They can improve spray characteristics by explosive vaporisation of the low boiling constituents in micelles c Pyrolysis with this method a substance can be converted into another using heat with the aid of a catalyst in the absence of oxygen or air With that a thermal decomposition of the oil takes place and the heaviest components of the oil are converted into lighter molecules which reduces the viscosity This method is also used to reduce viscosities of fuel oils and is known as visbreaking 10 d Transesterification it is the reaction of a fat or oil triglyceride with an alcohol to form esters and glycerol 3 After the reaction two products are obtained the main product is what is called biodiesel and the other is glycerol Of all the processes mentioned above the transesterification is the one that gives better results when the purpose is to reduce the viscosity of oils Furthermore glycerol which also has a commercial value is obtained as a by product 13 3 BIODIESEL 3 1 Definition The term Biodiesel was first used in 199
21. acid alkali catalysed reactions and of the potassium hydroxide catalysed reaction with standard conditions E Hemp oil WE Rapeseed oil acid Rapeseed oil alkali 120 90 60 30 0 Volume of glycerol mL Figure 6 5 Comparison of the volumes of glycerol obtained 490 0 467 5 445 0 422 5 Volume of biodiesel mL 400 0 Mi Hemp oil WE Rapeseed oil acid Rapeseed oil alkali Figure 6 6 Comparison of the volumes of biodiesel obtained 6 2 3 Influence of methanol The methanol experiments worked only when 20 methanol in volume was used for the reaction when using lower volumes the 3 27 test was not passed that is the reaction was incomplete Nevertheless not only was the reaction incomplete when 48 using low volumes of methanol the glycerol obtained was also very viscous making the sedimentation and separation steps complicated The reasons exposed above may indicate the necessity of using enough methanol on the reaction However methanol has several disadvantages when used in excess because it stays in both biodiesel and glycerol phases of the products Those products have to be cleaned of methanol because it is a dangerous product that can pollute the soil water etc Apart from that biodiesel standards set maximum methanol amounts in its composition and methanol should also be removed before using dry cleaning products To sum up a decision has to be taken with methanol There are basically two optio
22. and the biodiesel might not be recovered To set the air bubbling a hose is introduced in the lowest part of the separatory funnel After the stage time the bubbling is stopped the liquids are left to settle for about half an hour and then the water is extracted Afterwards either a new stage is started or the biodiesel is already prepared to be used It should be noted that it is important for the water after the last stage to be clean which means that all the impurities have already been eliminated It is also recommended for that reason the longest stage not to be the last because it is in that stage when the majority of the impurities are removed and the water will not be clear after that 4 5 Cleaning biodiesel with dry products 4 5 1 Equipment Weight balance Magnetic stirrer Erlenmeyer flask B chner funnel with elastomer adapter Kitasato flask Hose Vacuum pump Filter paper 4 5 2 Reagents Several different cleaning agents were tried more information about them can be found in the Annex V Magnesol D Sol Aerogel Raw biodiesel 29 4 5 3 Procedure The first step to take is to weigh the amount of drying product needed This will vary depending on the using instructions provided by the manufacturer In the case of the D Sol it is 0 5 in weight while for aerogel and magnesol it is 1 5 also in weight All the products are powder like solids Oil is added till the 100 in weight value is achieved
23. consumption habits but several other options are needed to achieve the objective of sustainability This paper focuses on biodiesel which is a natural substitute to mineral diesel Biodiesel is produced using different kinds of oil including edible and non edible vegetable oils waste vegetable oils residual oils used for cooking animal fats and algae oils Using a simple chemical procedure biodiesel can be produced Afterwards that biodiesel can be used blended with mineral diesel in different proportions or without blending what is called B100 in diesel engines Biodiesel is also suitable for direct burning There are several advantages when using biodiesel instead of mineral diesel the most important ones are the following e Itis an alternative to mineral diesel implying lower dependence on foreign imports of crude oil e Biodiesel is a renewable fuel e It has a favourable energy balance That is more energy is obtained when using biodiesel in a diesel engine than the amount that is used for the production of the biodiesel e Using biodiesel helps reducing greenhouse gas emissions as stipulated in the Kyoto Protocol agreement e Harmful emissions of biodiesel are lower than those of mineral diesel especially important in environmentally sensitive areas like large cities e Itis biodegradable and non toxic 1 There is a final reason that prompted writing this paper Most of the investigation work about biodiesel produ
24. content in the oil Preferred method if low grade oil is used Esterification and transesterification occur simultaneously Reaction can occur at mild reaction condition and less energy intensive Insensitive to FFA and water content in the oil Preferred method if low grade oil is used Esterification and transesterification occur simultaneously Easy separation of catalyst from product Preferred method if low grade oil is used Transesterification can be carried out at low reaction temperature even lower than homogeneous base catalyst Only simple purification step is required Sensitive to FFA content in the oil Soap will form if the FFA content in the oil is more than 2 wt Too much soap formation will decrease the biodiesel yield and cause problems during product purification especially generating huge amounts of wastewater Poisoning of the catalyst when exposed to ambient air Sensitive to FFA content in the oil due to its basicity property Soap will be formed of the FFA content in the oil is more than 2 wt Too much soap formation will decrease the biodiesel yield and cause problems during product purification Leaching of catalyst active sites may result in product contamination Very slow reaction rate Corrosive catalyst such as H2SO4 used can lead to corrosion on reactor and pipelines Separation of catalyst from product is problematic Complicated catalyst synthesis procedures lead to higher cost Normally high reac
25. form two different liquid phases After the separation raw biodiesel is obtained This product still contains several different compounds that should be eliminated residual catalyst water unreacted alcohol free glycerol and soaps Usually before the cleaning step methanol is removed using an alcohol stripper to prevent excess alcohol from entering the wastewater effluent in the case of the water cleaning and to follow the instructions marked by the producer when it comes to dry cleaning Both glycerol and alcohol can be easily removed by using water washing because they are highly soluble in water By using water residual salts and soaps can also be eliminated Water also helps to prevent the precipitation of saturated fatty acid esters and retards the formation of emulsions Different stages have to be done to wash the biodiesel which will 16 be washed when the water phase becomes clean Afterwards the water is separated from the biodiesel they can be easily separated due to their density difference Dry washing consists of using different products which will substitute the water in order to remove impurities In this case the free glycerol level is reduced and soaps are also removed The main advantage is the fact that no water is used eliminating any problems with wastewater effluents Among the different products that can be used commercial brands such as Magnesol or D Sol can be found 14 3 4 Characteristics of biodiesel
26. give a higher ester yield in a shorter time Usually when using acid catalysts higher molar ratios are needed probably because the use of acid catalysts is related to oils with high FFA content 21 When rapeseed oil is transesterified using potassium hydroxide as a catalyst the optimum molar ratio is 6 1 3 2 4 4 Catalyst concentration This parameter is highly affected by the kind of catalyst used different catalysts will require different concentrations Even if they belong to the same group as in the case of potassium hydroxide and sodium hydroxide different concentrations will be necessary to attain the same yields Therefore the optimum value for every catalyst will have to be determined by titration If the amount of catalyst is higher than the optimum there will be a decrease in the yield of methyl esters due to the formation of soap in presence of high amount of catalysts which apart from lowering the yield increases the viscosity of the reactants 11 3 2 4 5 Mixing Mixing is mandatory for the reaction to take place Without mixing the reaction only occurs in the interface between the methanol and the oil and it is very slow to be viable Therefore a mixing device is needed in the reactor used for the process 11 3 3 Cleaning raw biodiesel When the transesterification reaction is finished two products are obtained biodiesel and glycerol Both can be separated by sedimentation since due to their different densities
27. grease March 2005 BIODIESEL MAGAZINE 42 PROCESS feedstocks in BECON s pilot plant reac tor In both cases the methanol was removed from the methyl esters but not initially water washed First 20 gallons of the soybean methyl esters were water washed and dried while another 20 gallons were treat ed at 77 degrees Celsius with 1 percent by welght Magnesol After 20 minutes of mix ing longer than is probably required in a commercial plant setting Cooke said the purified methyl ester was filtered The resulting biodiesel from both methods passed all specifications of ASTM D 6751 According to the study s authors Van Gerpen and Kirk Menges the Magnesol treated biodiesel contained a lower soap and sodium content than the dried Magnesol treated and the biodiesel showed a significant improve water washed sample Furthermore ment in oxidative stability when compared to both the original methyl esters and the water washed and dried sample In a second trial 20 gallons of the yellow grease methyl esters were water washed and dried and 20 gallons were treated with at 77 degrees Celsius with 2 percent by weight Magnesol After 20 minutes of mixing the purified methyl ester was filtered Like the first test with soy methyl esters the Magnesol treated sample of yellow grease derived methyl esters passed all ASTM specifications while the waterwashed and dried sample did not The Magnesol treated biodies
28. maximum speed Afterwards the liquid that had to be purified or separated was added to the centrifuge using a funnel that was connected with a tube When the centrifuge was full enough the lightest liquid would leave by one of the sides while the heaviest compounds stayed inside the centrifuge until it was stopped 33 34 9 RESULTS 5 1 Titration Prior to the transesterification reaction the titration of the oils should be done to calculate the amount of catalyst which is necessary During the lab trials titrations with both potassium hydroxide and sodium hydroxide were done the results of both of them are shown in table 5 1 and table 5 2 Volume of 1g L KOH Grams of KOH L of oil Grams of KOH 500 mL mL of oil Type of oil Rapeseed 1 Rapeseed 2 Rapeseed 3 Sunflower Hemp Linseed Table 5 1 Titration results when using KOH as a catalyst Volume of 1g L NaOH Grams of NaOH L of oil Grams of NaOH S00 mL mL of oil Rapeseed 2 2 8 Table 5 2 Titration results when using NaOH as a catalyst Type of oil 6 3 Table 5 1 shows the results obtained when using potassium hydroxide as a catalyst while table 5 2 is for the sodium hydroxide In the first case three different types of rapeseed oil were tested and the second type was the one chosen to be the raw oil for all the experiments when rapeseed oil was used as a reagent The grams of catalyst for 500 mL of oil are shown because this is the volume of oil that was
29. obvious savings too MAGNESOL BIODIESEL MAGAZINE March 2005 Bertram said Magnesol actually offers the biodiesel producer a lot of latitude in running their process he said It adsorbs elycerin free glycerin metals soaps chlorophyll residual free fatty acids odors color methanol and water Since Magnesol adsorbs such a wide range of impurities it compensates for upstream upsets in the process offering clean and more stable biodiesel m For more information about Magnesol visit www dallasgrp com Tom Bryan is editorial director of Biodiesel Magazine Reach him by e mail at toryan bbibiofuels com or by phone at 701 746 8385 BIODIESEL MAGAZINE This article was printed in the 2005 March issue of Biodiesel Magazine PURIFICATION OF BIODIESEL AND OTHER HIGH PURITY ESTERS e Guarantee biodiesel quality ASTM D6751 e Reduce or eliminate water wash e Fliminate emulsions e Fxpedite purification process e Reduce energy requirements e Increase process yield e Improve storage stability OSI 06051203 BIODIESEL MA G A Z I N E January 2008 www BiodieselMagazine com TECHNOLOGY Cleaner and Clearer A In a challenging economic environment producing a top quality product is one way to maintain a competitive edge For biodiesel producers that means finding the most economical way to wash and polish their crude biodiesel to the highest possible standard Schroeder Ind
30. reaction without preparing the methoxide previously this was tried in one of the experiments at room temperature The results of the experiments are displayed in table 5 5 Amount of Vimethanol Reaction Voglycerol Molycerol Vbiodiesel Mbiodiesel Sample Voi mL 3 27 test KOH 9 mL time h mL e mL 2 BEE 6 8 500 100 6 93 96 8 480 419 8 Passed Table 5 5 Results obtained when the potassium methoxide was not previously mixed The reaction time is longer than usual due to some mixing difficulties that were observed at the beginning of the reaction 5 2 1 4 Adding the potassium hydroxide in two stages As an attempt to save catalyst the two thirds method was tried at room temperature Two different amounts of catalyst were tried 6 2 and 6 8 grams Amount of Vimethanol Reaction Vglycerol Mglycerol Vbiodieset Mbiodiesel Sample Voi mL 3 27 test KOH 9 oi mL m time h mL 9 mL 9 6 2 500 100 4 80 85 1 490 425 6 Passed 6 8 500 100 4 90 95 2 485 417 6 Passed Table 5 6 Results obtained when adding the potassium methoxide in two stages Stage 1 Stage 2 Sample Vmethoxide Reaction Valycerol M 0 V methoxide Reaction Volycerol M 0 mL time 1 mL glycerol 9 mL time h mL glycerol 9 66 2 96 60 34 2 24 25 66 2 61 64 1 34 2 29 31 1 Table 5 7 Volumes and masses of glycerol obtained 37 Both experiments were successful The reaction time was a bit shorter than usual because there
31. refers to the same type of product but due to an error in the first filtration two filter papers were used instead of one so the experiment was repeated Otherwise Aerogel 250 and Aerogel are different products and more information about them can be found in the Annex V Cleaning Seh Duration of ES Soap biodiesel Soap titration Soap biodiesel reduction tem stages h Be before g g after mL after 9 g mL soap RS stages before mL 3 4 3 4 3 4 MA 3 4 1 3 1 1 3 1 4 5 5 0 018 bubbling 2 0 0 7 0 006 0 002 63 6 87 3 AETS DaI 1 water 3 1 72 1 55 0 018 0 1 0 000 98 2 bubbling Table 5 18 Water cleaning results For the first water cleaned sample the soap titration was done twice one after 5 hours of cleaning 3 changes of water and the other after a new step which took 4 days The biodiesel cleaned with Magnesol was also cleaned with water afterwards in three steps 1 hour 72 hours 1 hour 5 5 Using the centrifuge Six different tests were done using the centrifuge some with just one component and others with two phase liquids Components Composition Result Sunflower oil Impurities were extractred Biodiesel glycerol 50 50 No separation of the liquids Biodiesel water 90 10 No separation of the liquids Raw biodiesel No impurities extracted Raw rapeseed oil No impurities extracted Raw glycerol No impurities extracted Table 5 19 Using the centrifuge 43 44 6 DISCUSSION 6 1 Titration Th
32. the manufacturers of diesel engines changed their specifications so as to make them more suitable for the viscosity of mineral diesel instead of the previously used vegetable oils There are several advantages in the use of vegetable oils as diesel which are portability ready availability renewability higher heat content lower sulphur content and lower aromatic content than that of mineral diesel and biodegradability 3 2 1 Constituents and properties of vegetable oils The oils and fats are mixtures of liquids Their main components of raw oils are usually triacylglycerols generally gt 95 as well as diacylglycerols monoacylglycerols and free fatty acids FFA Some other substances like phospholipids free sterols and sterol esters tocols triterpene alcohols hydrocarbons and fat soluble vitamins may also be present 4 The main difference between vegetable oils and animal fats is the fact that animal fats are usually saturated that is they do not have double bonds which makes them solid at room temperature On the other hand vegetable oils are usually liquid at room temperature The structure of vegetable oils differs from the structure of mineral diesel In the case of the vegetable oils as many as three fatty acids can be linked to a glycerol molecule using esters as linkers Such molecules are the main constituent mentioned above the triacylglycerols while the diacylglycerols and monoacylglycerols refer to the cases when o
33. used in all the experiments The difference between the three types of rapeseed oil is basically that they were stored in different containers and they had been obtained at different dates so the titration for the three of them had to be done 5 2 Biodiesel production 5 2 1 Influence of the catalyst As it has been previously explained the catalyst is one of the most important factors affecting the reaction The next sections will show the influence of different catalysts and the way of using them when doing the transesterification reaction All the reactions were done at room temperature which was approximately 21 C 35 5 2 1 1 Amount of potassium hydroxide Amount of Vmethano Reaction Vglycerol Mglycerol Vbiodieset Mbiodiesel Sample Voi ML 3 27 test KOH g mL time h mL 9 mL 9 500 100 5 92 93 7 480 415 9 Not passed 500 100 5 92 91 3 495 425 6 Not passed 500 100 5 94 96 9 490 421 9 Passed 500 100 5 92 95 1 475 409 7 Passed 500 100 5 103 105 1 475 419 3 Passed Table 5 3 Influence of the amount of potassium hydroxide in the production of biodiesel Five different amounts of potassium hydroxide were tried in all the cases the rest of factors were the same In table 5 3 it can be seen that only three out of five experiments were successful that is passed the 3 27 test This indicates that a minimum amount of 6 8 grams of KOH is necessary to obtain a complete reaction Therefore that amount was decided
34. 00 5 106 108 3 460 397 5 Passed 60 6 8 500 100 5 jo Seis 395 344 1 Passed Table 5 11 Influence of the temperature on the transesterification reaction First of all it should be mentioned that all the trials passed the 3 27 test therefore the oil was fully reacted in all the cases The results show clearly the difference in the yield of biodiesel with the temperature when long reaction times ares used With higher temperature higher glycerol yields and lower biodiesel yields are obtained 490 L 460 430 400 Biodiesel volume m Bst gt gt gt room AO 60 Temperature C Figure 5 5 Evolution of the volume of biodiesel with the temperature In this experiment the results of the solubility test have certain importance too Those results were better when the temperature was lower Since the amount of glycerol obtained at 60 C was found to be too high a new reaction was started with the difference that in this case the reaction time was set to just an hour Amount of Vmethano Reaction Voglycerol Moiycero Vbiodiesel Mbiodiesel Sample T C KOH g Voi mL 3 27 test mL time h mL 9 mL g 100 83 87 1 480 419 8 Passed 500 Table 5 12 Biodiesel production at 60 C after 1 hour The 3 27 test was passed which indicates that the reaction was complete 40 Another trial was done at low temperatures Due to technical difficulties it had to be done outside stirri
35. 2 in the National Soy diesel Development Board now called National Bio Diesel Board in the United States 10 Biodiesel is the name used to refer to a diesel equivalent fuel that has been obtained from biological sources 4 using the transesterification reaction Chemically biodiesel is a mixture of methyl esters with long chain fatty acids and is typically made from nontoxic biological resources such as vegetable oils animal fats or even waste vegetable oils WVO 14 3 2 Transesterification process For the production of biodiesel a vegetable oil or animal fat reacts with ethanol or methanol in the presence of a catalyst From this methyl or ethyl esters are obtained which are the components of biodiesel Along with the esters glycerol is also produced 3 That reaction is called transesterification Stoichiometrically when the reaction takes place for every mole of triglycerides reacting three moles of alcohol are used However a higher molar ratio of alcohol is usually used for maximum ester production 13 This will be more precisely explained in the next pages of the report CH O CO R CH OH R O CO R l Catalyst CH O CO R 3ROH CH OH R O CO R CH O CO R CH OH R O CO R Triglyceride Alcohol Glycerol Mixture of fatty acid esters Figure 3 1 Chemical equation of the transesterification mechanism 14 Ri R2 and R3 are long chain hydrocarbons sometimes they are also known as fatty acids
36. 5 Ext 5 Kir i RETINE Pr ee as bd i fy ee p Be aa ee E id E es A RAPESEED METHYL ESTERS Initial Sample None 637 30 0 0 020 max 0 053 0 000 A 0 217 0 162 120 min 90 130 5 0 max 53 3 5 0 max 6 5 6 0 min 0 65 500 max 0 020 max 0 2 max EMAIL biodiesel dallasgrp com Washed 0 5 D SOL amp Dried D60 SOYBEAN METHYL ESTERS Washed 0 5 D SOL amp Dried D60 YELLOW GREASE METHYL ESTERS Initial Washed 1 5 D SOL Sample And Dried D60 Initial Sample 651 le 0 1900 GI 0 0 033 0 002 0 000 0 063 0 209 0 196 0 186 0 220 80 143 1150 100 61 J 0 6 4 0 0 8 05 0 6 3 0 5 DALLAS WEB www dallasgrp com SPECIALTY ADSORBENTS 07051205 With a solid track record in oleo chemical purification The Dallas Group has entered the biodiesel industry with a synthetic magnesium silicate adsorbent that has changed the way some producers clean up their methyl esters By Tom Bryan he Dallas Group of America Inc a recognized leader in oleo chem ical purification technology is arguably the only U S company actively marketing a commercial product for the adsorptive purification of biodiesel The company s synthetic magnesium silicate adsorbent sold under the trademarked name Magnesol is an adsorbent filter aid that ensures biodiesel quality by removing contaminants within methyl esters Subsequently the removal of con taminants enables biodiesel producers to guarantee t
37. ATION DOT CLASS Not Regulated UN NA NO Not Classified FREIGHT CLASSIFICATION NMFC 48210 Column 55 IMO CLASS Not Classified ADR RID Not Classified Comply with all EU national and local regulations 15 REGULATORY INFORMATION This substance is not classified as dangerous according to EU Directive 67 548 EEC This material is not listed in Sections 302 312 or 313 of US SARA III It is reported in the US TSCA Inventory 1986 This substance has been pre registered under REACH A Chemical Safety Assessment has not yet been carried out for this substance 16 OTHER INFORMATION Approximate chemical formula MgO 2 6SiO International Numbering System INS number 5531 European Union E number E553a i EINECS number 215 681 1 References A through D are specific to synthetic magnesium silicate with the approximate chemical formula MgO 2 6SiO A 21 CFR Part 182 Subpart C Generally recognized as safe B Clinical Toxicology of Commercial Products Edition 4 1976 No acute toxicology recognized C NIOSH Registry of Toxic Effects of Chemical Substances Vol 2 1986 Irritation data Human skin 300 micro gram 3 days Very mild D Magnesium silicate with an approximate chemical formula of MgO 2 6SiO is not listed in IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man 1988 Industrial Hygiene and Toxicology F A Patty Industrial Toxicology Alice Hamilton a
38. After the transesterification reaction and the cleaning biodiesel is obtained It is a clear amber yellow liquid Due to the conversion of triglycerides into esters the molecular weight of biodiesel is one third of the triglyceride the viscosity is reduced by a factor of about eight and the volatility is also increased This means that the viscosity of biodiesel is similar to the viscosity of diesel fuels It should also be noted the fact that the esters of biodiesel contain 10 11 oxygen by weight resulting in more combustion in an engine than hydrocarbon based diesel fuels The cetane number of biodiesel is around fifty Biodiesel is considered as a clean fuel because it has no sulphur or aromatics and its content in oxygen which is helpful to burn it completely Due to its higher cetane number it improves the ignition quality even if it is blended with mineral diesel 10 lt has better lubricant properties than diesel fuel It is also non toxic and biodegrades quickly The associated risk of handling transporting and storing biodiesel is lower than that of mineral diesel 3 Table 3 4 shows a comparison of different fuel properties of petrodiesel and biodiesel Fuel Property Test method ASTM D975 Diesel ASTM D6715 Biodiesel Flash point D 93 325 K min 403 K Water and sediment D 2709 0 05 max vol 0 05 max vol Kinematic viscosity at 313 K D 445 1 3 4 1 mm2 s 1 9 6 0 mm2 s Sulphated ash D 874 0 02 max wt Ash D 482 0 01 max wt
39. GHTING MEASURES EXTINGUISHING MEDIA D SOLO 300 R is not explosive flammable or combustible Select the proper media to extinguish a surrounding fire 6 ACCIDENTAL RELEASE MEASURES SPILL CLEANUP METHODS Dry material can be swept or shoveled up Avoid generating dust Flush residue with water Observe environmental regulations Make sure that all personnel involved in housekeeping and spill clean up follow good industrial hygiene practices and wear proper personal protective equipment 7 HANDLING AND STORAGE USAGE PRECAUTIONS None in designated use STORAGE PRECAUTIONS None in designated use STORAGE CRITERIA Do not store in aluminum container or use aluminum fittings or transfer lines as flammable hydrogen gas can be generated 8 EXPOSURE CONTROLS AND PERSONAL PROTECTION VENTILATION No special requirements RESPIRATORS Wear a NIOSH MSHA approved dust mask where airborne contaminants occur PROTECTIVE GLOVES Wear chemical resistant gloves such as rubber neoprene or vinyl EYE PROTECTION Chemical goggles OTHER PROTECTION Full cover clothing HYGIENIC WORK ROUTINES 9 PHYSICAL AND CHEMICAL PROPERTIES Magnesium silicate Component B Physical State 68 F White powder White powder Melting Point 3470 F Absolute Density H20 1 2 10 2 20 Solubility in Water insoluble complete Vapor Pressure N A N A Viscosity N A N A Boiling Poin
40. In the presence of the catalyst the alcohol molecule will be able to break the fatty acid chains resulting in two different products glycerol and a mixture of fatty acid esters 14 3 2 1 Reagents As shown in the reaction above two reagents are needed oil and an alcohol The decision of which oil and which alcohol to use will depend on many different factors In both cases the availability of some kind of oil and or alcohol will probably define which one to use However in many cases when the reagents to use have to be chosen many different aspects have to be taken into account In the case of the alcohol probably the most important reason is the money Ethanol and methanol are the most commonly used alcohols but methanol is usually preferred because it is cheaper 15 Moreover ethanol has a lower transesterification reactivity than methanol 14 Of course other alcohols could be considered but their higher prices make them unsuitable except for the cases when there is a cheap source available Choosing the oil is probably a more complex issue than choosing the alcohol In this case many different factors have to be taken into account not only the price When commenting on the price it should be noted that the lower the price the lower the quality of the oil Usually lower price means a high content of FFAs which as will be shown in the next chapters involves a bigger production of soap a by product that is not interesting
41. OP2 1 4hp OFS 1 2hp 1PO 1hp 2P0 2hp Input Voltage 1 100 120VAC 2 200 240VAC Series Name 1 800 633 0405 GS1 Series Specifications 115V 230V CLASS GS1 Series Model GS1 10P2 GS1 10P5 GS1 20P2 GS1 20P5 GS1 21P0 GS1 22P0 Price es gt gt lt gt lt gt lt gt 1 4 hp 1 2 hp 1 4 hp 1 2 hp thp 2hp Motor Rating 0 2 kW 0 4 kW 0 2 kW 0 4 kW 0 7 kW 1 5 kW Rated Output Capacity 200V kVA 0 6 1 0 0 6 1 0 1 6 21 eae i a Three phase 200 Rated Input Voltage single phase 100 120 VAG 10 Single three phase 200 240 VAC 10 50 60 Hz 5 240 VAC 10 50 60 Hz 5 50 60 Hz 5 Three phase corresponds to double the Rated Output Voltage Three phase corresponds to the input voltage input voltage Soft Rated Input Current A 6 9 4 9 1 9 6 5 2 7 9 7 5 1 al Rated Output Current A 1 6 25 1 6 25 4 2 Moors amp earDoX Watt Loss 100 I W 18 4 26 8 44 6 Weight kg Ib 2 20 2 20 2 20 en Dimensions HxWxD mm in 132 0 x 68 0 x128 1 5 20 x 2 68 x 5 04 i otor Accessories Controls Ethernet Communications module for GS Series GS EDRV ai Drives DIN rail mounted Sensors Four port RS 485 multi drop termination board GS RS485 4 E Eight port RS 485 multi drop termination board GS RS485 8 u Software GSoft KEP Direct Limit Switches OPC Server KEP Direct Encoders Current Sensors Pressure Sensors Temperature Sensors Pushbutt
42. OR OF ANY NATURE IS MADE WITH RESPECT TO ANY PRODUCT REFERRED TO HEREIN THE DALLAS GROUP OF AMERICA INC DOES NOT ASSUME RESPONSIBILITY AND EXPRESSLY DISCLAIMS LIABILITY FOR LOSS DAMAGE OR EXPENSE ARISING OUT OF OR IN ANY WAY CONNECTED WITH THE HANDLING STORAGE USE OR DISPOSAL OF THE PRODUCTS REFERRED TO HEREIN The data contained herein is being supplied for the limited purpose of complying with the OSHA Right to Know Regulation 29 CFR 1910 1200 The submission of this MSDS may be required by law but this is not an assertion that this substance is hazardous when used in accordance with proper safety practices and normal handling procedures FOR MORE INFORMATION CALL 812 283 6675 Revised 08 2 09 The Dallas Group of America Inc 374 Route 22 P O Box 489 Whitehouse NJ 08888 1 908 534 7800 1 908 534 0084 fax www dallasgrp com MATERIAL SAFETY DATA SHEET Conforms to CFR 1910 1200 1 IDENTIFICATION OF SUBSTANCE PRODUCT NAME D SOLO GRADES 300R SUPPLIER The Dallas Group of America Inc 374 Route 22 P O Box 489 Whitehouse NJ 08888 Tel 908 534 7800 FAX 908 534 0084 Information department Product Safety Department 2 COMPOSITION DATA ON INGREDIENTS Component CAS No Approximate Magnesium Silicate 1343 88 0 70 Component B 30 The identity of Component B is being withheld as a trade secret per 29CFR 1201 12 i 3 HAZARDS IDENTIFICATION D SOL 300R has no
43. age seal failures filter clogging and deposits at injection pumps Its lower volumetric energy density means that more fuel needs to be transported for the same distance travelled when using biodiesel than when using diesel lt can cause dilution of engine lubricant oil requiring more frequent oil change than in standard diesel fuelled engines A modified refuelling infrastructure is needed to handle biodiesel which adds to its total cost 10 21 22 4 EXPERIMENTAL PROCEDURE For the realisation of this thesis several different laboratory procedures were carried out In this section all of them will be explained in detail More information about the equipment used for the experimental procedure can be found in the Annex III 4 1 Titration Before starting the biodiesel production a test has to be performed This test is called titration and it is used to determine the amount of free fatty acids present in the oil This is compulsory to determine the amount of catalyst needed for the reaction 4 1 1 Equipment The equipment needed for the titration is Magnetic stirrer Burette Plastic and volumetric pipettes Pipette bulb Volumetric flask Weight balance Erlenmeyer flask 4 1 2 Reagents The following reagents are needed to perform the titration Water Potassium or sodium hydroxide Phenolphthalein Isopropyl alcohol Vegetable oil 4 1 3 Procedure The first step to take will be pr
44. and then the mixture is stirred for twenty minutes After that time a vacuum filtration is done using the B chner funnel the Kitasato flask and filter paper The filtration is done twice using the same paper where a cake of powder has been created which once created will act as the filtering medium When the second stage of the filtration is finished the biodiesel is cleaned and ready to be used 4 6 3 27 test 4 6 1 Equipment Pipettes Pipette bulb Test tubes 4 6 2 Reagents Methanol Raw biodiesel 4 6 3 Procedure The 3 27 test also called Jan Warnquist test after its developer is used to find the degree in which triglycerides are converted into methyl esters in the transesterification reaction Therefore with this test the development of the reaction can be known To perform the test methanol and raw biodiesel are needed First 27 parts of methanol are put into a test tube Afterwards three parts of raw biodiesel are added and the content of the tube is agitated After a resting period of 30 minutes it can be checked whether any precipitate has appeared if there is precipitate the test has not been passed meaning that the reaction is not complete If the test is performed properly and a batch of fuel passes there is no visible precipitate then the fuel is likely to be converted very close to the ASTM standard for conversion of 0 24 total glycerides or better 27 30 4 7 Solubility test 4 7 1 Equip
45. arch different tests were made to understand the results obtained and improve the method Finally when the all the tests were performed the results were analysed and the best method to produce biodiesel without using heat was determined This will allow implementing the process at a bigger scale 1 5 Outline The first section of the thesis which is called Vegetable oils as fuels is an introductory section in which it is explained the properties of vegetable oils and their constituents as well as their sources Apart from that a justification for them not being used directly as fuels is given when talking about their disadvantages Finally different methods to improve the properties of vegetable oils for using them as fuels are explained including transesterification Next comes a comprehensive chapter about biodiesel In it apart from defining what biodiesel is the transesterification reaction is explained thoroughly including reagents catalysts mechanism and conditions Besides there is an explanation on how to clean biodiesel including both dry and water cleaning and all the characteristics of biodiesel are stated Eventually the advantages and disadvantages of biodiesel are displayed The third chapter is the experimental procedure As its name says what was done in the lab is explained step by step following the order of the biodiesel making process lt starts 3 with the titration Then comes the production of biod
46. ay screens and can be downloaded to a computer for real time monitoring and batch tracking The system can also send e mail alerts and even download alerts to cell phones Archiving traceability building up records having control of your produc tion process is absolutely important Benzies says If someone has problems with their vehicle they instinctively blame the fuel That s one of the things producers have to keep in mind they need to have some sort of in house traceability that says that that particular batch was a good batch Performance Magnesol was compared with wet washing by researchers at lowa State University Benzies says The results showed significant results after just 20 minutes of processing The perform ance data showed a massive decrease in glycerin and the moisture removal capa bility and methanol reduction he says More importantly if you look at the soap reduction capability its just stag gering in a short space of time to get from a high level to an acceptable level That embraced this dry wash medium is one of reasons we have The dry wash systems have other benefits The cost of operating a dry wash system is lower than a wet wash system Disposal and water treatment costs are also lower with a dry wash sys tem Lower cost is not the biggest sell www BiodieselMagazine co The BD 6000 Final Polishing Unit can be outfitted with Schroeder Particle and Moisture m
47. be available in those areas Increased income taxes Biodiesel as any other fuel is charged with taxes by the government which receive more income taxes if biodiesel is used Increased investments in plant and equipment For the production of biodiesel it is necessary to build production plants and buy equipment Agricultural development As in the case of the rural manufacturing jobs since it is necessary to grow the seeds this will mean that the agriculture in the area will develop International competitiveness While the petroleum reserves are concentrated in just a few countries in every country of the world biodiesel can be produced Due to this many countries could be able to join the fuels market which would make it more competitive 18 Reducing the dependency on imported petroleum The reason is fundamentally the same as the stated above biodiesel can be produced by any country and being a substitute for diesel there will be a lower necessity to import it Inherent lubricity The esters forming biodiesel have been analysed and it has been found that they show good potential as base stock in biodegradable lubricant formation Higher cetane number As shown in Table 3 4 biodiesel has a higher cetane number than diesel 22 23 24 25 3 5 1 2 Environmental impacts Greenhouse gas reductions Complete combustion of diesel fuel releases 3 11 kg of CO2 per kilogram while biodiesel releases 2 86 kg Moreover the carbon di
48. blications or other uses and permissions January 2008 January 2008 TECHNOLOGY www BiodieselMagazine co m lake water out of the equation MAGNESOIL eliminates the need for water wash and Purify biodiesel in minutes not hours and with no messy emulsions No need for expensive centrifuges dryers or settling tanks No drying required No water permitting No expensive water pre treatment or post treatment systems DIS 1 812 283 6675 Ext 5 BIODIESEL M A G A Z I N E Biodiesel Magazine 2008 ARTICLE WAS PRINTED IN JANUARY 2008 ISSUE OF BIODIESEL MAGAZINE biodiesel dallasgrp com folks so we are trying to explain to them how it works and why it works and how it can save them money But it s coming along Tightening water supplies plus the cost of treating effluent in many areas of the United States will be a factor in biodiesel production Dugan says He described a visit to a biodiesel producer who used wet washing largely because he had a favorable agreement with the municipal water and sewer service providers They said if the local municipality hadn t been so gracious in helping to get the business started they would have had to go to Magnesol and a dry wash process he says When they build their next plant it may be a different story It has everything to do with the local rules and government Despite the current challenges in the biodiesel industry
49. by its price but some other factors should also be studied Nevertheless the amount of free fatty acids in the oil is a good point to start with because it may cause several difficulties when making biodiesel Therefore using oil with low FFA content is always recommended Since the cost of raw materials accounts for about 60 80 of the total cost of biodiesel production choosing a right feedstock is very important 10 11 3 2 2 Catalyst The presence of a catalyst is mandatory for this chemical reaction to happen in normal conditions Several types of catalysts have been tried both heterogeneous and homogeneous The homogeneous catalysts can be divided into two categories alkalis and acids The most common alkali catalysts are potassium hydroxide potassium methoxide sodium hydroxide and sodium methoxide Alternately the acid catalysts include products like sulphuric acid hydrochloric acid and sulphonic acid The other group is formed by heterogeneous catalysts It includes enzymes titanium silicates alkaline earth metal compounds anion exchange resins and guanadines heterogeneisated on organic polymers 1 A third option is also available it is using supercritical methanol In this case no catalyst is needed but on the other hand high temperature and high pressure conditions e 573 K and 20 MPa are needed 13 Another option that should be mentioned is the use of ultrasonic reactors and microwaves Ultrasonic react
50. c adsorptive sites as Opposed to passive filter aid type materials like diatomaceous earth which did not have any active filtration sites With the use of Magnesol Cooke said the producer is left with a potentially valuable filter cake rather than dirty effluent Clients of The Dallas Group are currently exploring a variety of markets for this filter cake and the company believes the byproduct has potential value as an animal feed supplement a form of biomass fuel fertilizer or compost The BECON study The Dallas Group has over 30 years experience in the purification of various chemicals including esters and the result ing byproducts of those processes In addition to its own in house work on biodiesel with outside lab confirmation the Biomass Energy Conversion Facility BECON at lowa State University per formed trials comparing the traditional water wash method to biodiesel purifica tion with Magnesol Results from this study were discussed by Cooke in his presentation and also by Dr Jon Van Gerpen during a special technology ses sion at the National Biodiesel Conference Van Gerpen a respected authority on the subject of biodiesel directed the pilot study at the BECON facility He has since taken a position at the University of Idaho as department head of Biological and Agricultural Engineering In that study methyl esters were pro duced in 40 gallon batches from both degummed soybean oil and yellow
51. catalysts as well as with different ways of adding the catalyst As for the cleaning good results were obtained with both dry products and water cleaning since the soap content of the biodiesel was reduced in both cases Apart from that the centrifuge proved to be valid to eliminate impurities from raw oil TABLE OF CONTENTS 1 INTRODUCTION 1 1 Background 1 2 Purpose 1 3 Limitations 1 4 Method 1 5 Outline 2 VEGETABLE OILS AS FUELS 2 1 Constituents and properties of vegetable oils 2 2 Sources of oils and fats 2 3 Disadvantages of vegetable oils when used as fuels 2 4 Methods to improve the quality of vegetable oils 3 BIODIESEL 3 1 Definition 3 2 Transesterification process 3 2 1 Reagents 3 2 2 Catalyst 3 2 3 Mechanism 3 2 4 Reaction conditions 3 3 Cleaning raw biodiesel 3 4 Characteristics of biodiesel 3 5 Advantages and disadvantages of biodiesel 3 5 1 Advantages of biodiesel 3 5 2 Disadvantages of biodiesel 4 EXPERIMENTAL PROCEDURE 4 1 Titration 17 18 18 20 23 23 4 1 1 Equipment 4 1 2 Reagents 4 1 3 Procedure 4 2 Transesterification reaction 4 2 1 Equipment 4 2 2 Reagents 4 2 3 Procedure 4 3 Separation of the products 4 3 1Equipment 4 3 2 Procedure 4 4 Cleaning biodiesel with water bubbling 4 4 1 Equipment 4 4 2 Reagents 4 4 3 Procedure 4 5 Cleaning biodiesel with dry products 4 5 1 Equipment 4 5 2 Reagents 4 5 3 Procedure 4 6 3 27 test 4 6 1 Equipment 4 6 2 Reagents 4 6 3 Procedure 4 7 Solubility test 4
52. category Ill irritation clearing in 7 days or less The above study was performed by Hill Top Biolabs Inc Cincinnati OH in 1989 and was specific to magnesium silicate with the formula MgO 2 6SiO The conclusions of this test were a Magnesium silicate is classified as non toxic by oral administration b Itis not a primary skin irritant or a corrosive by dermal application c Itis not classified as toxic by dermal administration d Itis classified in Toxicity Category III by ocular administration 11 TOXICOLOGICAL INFORMATION continued Component B OSHA Permissible Exposure Limit PEL and ACGIH Threshold Limit Value TLV have not been established The recommended ceiling limit is 2 mg m respirable dust This product does not contain any ingredient designated by IARC NTP ACGIH or OSHA as probable or suspected human carcinogens 12 ECOLOGICAL INFORMATION D SOL 300R is inorganic and not subject to biodegradation There is no data available on the environmental fate of this material Magnesium silicate is not a known pollutant Component B is not a listed toxic chemical under SARA Ill 8302 8304 or 8313 The high pH alkalinity of the undiluted or unneutralized material is harmful to aquatic life 13 DISPOSAL CONSIDERATIONS DISPOSAL METHODS The components of D SOL 300R are not regulated under RCRA landfill requirements However unneutralized material is a RCRA Ha
53. cation reaction However it was also observed that it took longer to start the reaction in this case because of the increased difficulty to dissolve the flakes of potassium hydroxide This is why the reaction time chosen was longer than in the previous cases to allow the reaction to be complete It can be observed from the results that the products obtained are similar to what is obtained with previous mixing 46 T 375 E oO 250 2 125 Glycerol Biodiesel BE Previous mixing ES Without previous mixing Figure 6 3 Comparison of volumes with previous mixing of the methoxide and without it 500 0 375 0 D 8 250 0 q gt 125 0 Glycerol Biodiesel Hi Previous mixing ES Without previous mixing Figure 6 4 Comparison of masses with previous mixing of the methoxide and without it As it can be seen in figures 6 3 and 6 4 both volumes and masses are almost equal when previous preparation of the methoxide was done and when it was not done This means that the reaction could be done without preparing the methoxide previously at least when using potassium hydroxide as a catalyst However this was done with 500 mL of oil it may imply more difficulties when doing it with big volumes because of the complications with the stirring 6 2 2 4 Adding the potassium hydroxide in two stages This experiment was successful because the 3 27 test was passed when using both 6 2 and 6 8 grams of potassium hydroxide It is important to note that
54. chnik Having looked at various dry wash systems including competitive silicates and resin systems we decided to run with the Magnesol product based on several fac tors first and foremost it s one of the few products that had independent ver ification put on it Benzies says It s one of the few products that published performance data which is absolutely vital Keeping Watch Schroeder s system works in a simi lar fashion to other dry wash systems see Adsorbing It All in the March 2005 issue After crude glycerine is sep arated and removed and excess methanol is vented Magnesol powder is added to a tank of biodiesel and agitat ed with a mixer for about 25 minutes The process uses 0 5 percent to 1 per cent Magnesol by weight depending on the level of contaminants in the batch of biodiesel So 2 000 pounds of biodiesel which is about 265 gallons would require 20 pounds of Magnesol The powder attracts polar molecules and separates them from the nonpolar biodiesel Methanol water glycerin and catalysts are all polar molecules That s effectively what happens when the Magnesol comes in contact with the crude methyl ester Benzies says It adsorbs all the impurities After agitation the biodiesel is cir culated through Schroeder s wash columns to filter out the Magnesol and its cargo of contaminants Moving across to the wash stage it is at this time when we start to see t
55. ction has been carried out in a way that makes heat necessary for obtaining it Therefore no data could be found in the literature for the process taking place at room temperature However due to the importance of small scale biodiesel producers it would be very interesting if a process avoiding the use of heat was developed In that way both the equipment and the control of the process could be easily simplified allowing everyone to produce their own biodiesel without too many complications In response to this lack of information this thesis is an attempt to prove that there is no need to use heat in order to produce biodiesel 1 2 Purpose The aim of this thesis is to explain what biodiesel is and to find the best conditions for producing biodiesel avoiding the use of heat lt includes the best reaction parameters as well as cleaning and purifying methods 1 3 Limitations The main limitation of this project is the difficulty to determine the quality of the produced biodiesel To do so gas chromatograph equipment is needed unfortunately there was no such equipment available which has determined the final results Therefore it has not been possible to find out whether the produced biodiesel fulfils the specifications However some other simple tests have been used and the obtained results are positive lt should also be mentioned that the economic aspect has not been given a foremost importance when conducting the investigation Thus
56. d of the oil era For several years warnings about the depletion of the oil reserves have been transmitted However nowadays that is not a reality or at least it is not a public reality It is almost impossible to determine how long it will be possible to live in the petroleum era Nevertheless it is a reality that eventually the problem will have to be faced As if that was not enough lately a new and very worrying matter has emerged the global warming It is believed that due to the high dependancy on fossil fuels the amount of carbon dioxide in the atmosphere is increasing Thus creating what is called the greenhouse effect that prevents heat in the form of infrared radiation from leaving the earth Because of this the earth temperature is said to be increasing this could cause several environmental catastrophes and maybe even change the earth as we know it now One of the options to reduce our effect on the global warming and at the same time minimise the oil dependency are biofuels Biofuels have two advantages when compared to other energy sources they are a renewable source of energy and they minimise the carbon dioxide emissions Therefore when using them using oil and the troubles related to it are avoided It must be said that biofuels are not the only solution Actually biofuels should never be regarded as if they were the solution to all problems Biofuels are just one of the new energy sources that can change our energy
57. e of the substance Adsorbent filter aid flow agent 1 3 Supplier The Dallas Group of America Inc 374 Route 22 P O Box 489 Whitehouse NJ 08888 Tel 908 534 7800 FAX 908 534 0084 Information department Product Safety Department 1 4 Emergency Telephone Not required for non hazardous substances 2 HAZARDS IDENTIFICATION Magnesium silicate is not explosive flammable or combustible It is a mild irritant to eyes skin and respiratory passages see Section 11 Not classified as dangerous under EU Directive 67 548 EEC O Health HMIS ratings scale 0 4 Health 0 Fire 0 Reactivity O 3 COMPOSITION DATA ON INGREDIENTS CAS No EINECS No Description 1343 88 0 215 681 1 Magnesium Silicate 97 100 4 FIRST AID MEASURES Inhalation Drink water to clear the throat blow nose to clear respiratory passages Ingestion Incidental ingestion of this product does not require first aid Skin Contact Wash exposed area thoroughly with soap and water Eye Contact Flush eyes with plenty of water Call a physician if irritation persists 5 FIRE FIGHTING MEASURES EXTINGUISHING MEDIA Select the proper media to extinguish a surrounding fire No special protective equipment for firefighters is required 6 ACCIDENTAL RELEASE MEASURES SPILL CLEANUP METHODS Sweep or vacuum spilled material The use of a sweeping compound dust suppressant is suggested Make sure that all personnel i
58. e of water 19 Carbon sequestration As explained above when biodiesel crops are grown the plants fix carbon dioxide Lower sulphur content Biodiesel contains less sulphur than diesel which means lower sulphur emissions Lower aromatic content As in the case of the sulphur the aromatic content of biodiesel is lower than that of mineral diesel leading to lower aromatic emissions Pure biodiesel 20 Biodiesel 80 petrodiesel Emission type B100 B20 Total unburned hydrocarbons HC 67 20 Carbon monoxide 48 12 Particulate matter 47 12 NOx 10 2 Sulphates 100 20 Polycyclic aromatic hydrocarbons 80 13 Table 3 6 Average biodiesel emissions compared to conventional diesel according to EPA 2002 Less toxicity Biodiesel is non toxic 22 23 24 25 3 5 1 3 Energy security Domestic targets Using biodiesel helps achieve targets in domestic fuel production Supply reliability Since it can be produced locally the reliability of the supply is higher than that of internationally obtained products Higher flash point It has a higher flash point than diesel and that makes it less dangerous because it evaporates with more difficulty Reducing use of fossil fuels Being a direct substitute of diesel it reduces its use Ready availability Production of biodiesel takes the time necessary to grow the crop make the oil and then the biodiesel Even if it may take a year compared to the time that
59. e parameters the methodology used was very simple Fixed amounts of rapeseed oil and methanol were used 500 mL for the rapeseed oil and 100 mL for the methanol while the amount and type of catalyst was varied The amounts of both potassium and sodium hydroxide in the first trials were the obtained on the transesterification Afterwards lower and higher amounts were tried The first step before starting the reaction was mixing the catalyst and the alcohol using the stirrer Afterwards this compound called methoxide was combined with the oil using stirring again during the whole reaction period The reaction time was set to 5 hours and the temperature that of the room which was 21 C approximately This means that no heat was used 4 2 3 2 Amount of methanol This case was an attempt to determine whether or not it was possible to use reduced amounts of methanol for the reaction Therefore the amount of methanol was the only changing factor while all the others were kept constant Lower values than 100 mL were tried The conditions used were 6 8 grams of potassium hydroxide 500 mL rapeseed oil 5 hours as reaction time continuous stirring and room temperature Once again the potassium methoxide was prepared before the actual reaction started and then it was added to the oil 4 2 3 3 Reaction temperature Despite the fact that the purpose of the thesis is using no heat for the transesterification reaction some trials were carried out us
60. e precipitated silica material shows great similarities with the classic silica aerogel invented already in the 1930 s but involves a less complicated route of processing higher flexibility and the use of cheaper feedstock chemicals Depending on the application the material can be made as a filler material with a typical size range of 5 75um or as coarser aggregates or granules having a characteristic size of up to 10mm The specific surface area BET area is typically 400m2 g The bulk density of granules as well as filler is typically less than 0 40kg m3 The substrate material is environmentally friendly and consists solely of benign chemicals and common elements such as Si Ca and Mg Two different materials were used in the biodiesel trials one of them is a spray dried magnesium silicate material which has a particle range of 5 75 micrometers The other material is a calcium magnesium 35 65 silicate impregnated with 8 potassium hydroxide and a particle range smaller than 250 micrometers The Dallas Group of America Inc 374 Route 22 P O Box 489 Whitehouse NJ 08888 1 908 534 7800 1 908 534 0084 fax www dallasgrp com MATERIAL SAFETY DATA SHEET Conforms to US CFR 1910 1200 and REACH EC 1907 2006 Date of Issue March 9 2009 1 IDENTIFICATION OF SUBSTANCE 1 1 PRODUCT NAME MAGNESIUM SILICATE synthetic amorphous hydrous TRADE NAME D SOL GRADES D Series 1 2 Us
61. e results of the titration showed clear variations on the amounts of free fatty acids of the different oils This may be caused by the composition of the oil but also because of long storage times which usually lead to decomposition of the triglycerides and thus more content of free fatty acids 30 0 22 5 15 0 1 9 grams of KOH L of oil 0 Mi Rapeseed 1 EI Rapeseed 2 Rapeseed 3 BI Sunflower Ml Hemp EI Linseed Figure 6 1 Comparison of the titration results of the different oils 6 2 Biodiesel production 6 2 1 Reaction time Even if specific experiments to determine the most appropriate reaction time were not performed it was determined that 5 hours was the best value for most of the reaction times This is because it is enough time for the reaction to be complete The only limitation imposed by the reaction time is that in case it is not long enough the reaction will not be complete Therefore allowing a long enough time will avoid any problems and ensure a complete reaction 6 2 2 Influence of the catalyst 6 2 2 1 Amount of potassium hydroxide Several difficulties were found in the first attempts to obtain a fully reacted biodiesel Therefore five different amounts of catalyst were tried This indicates that the titration results may not always be completely correct However it can be used as a Starting point Especially if large volumes of biodiesel are to be produced at a time it is recommended to try the reac
62. eactions In this case there was an important difference between the two reactions in the case of hemp oil 100 mL of methanol were used in the second stage while only 50 mL were used with the rapeseed oil This was done to try whether or not it was possible to use only 50 mL in the second stage because 50 more had already been used in the first one As it can be seen in the results the product obtained from the rapeseed reaction is not completely transesterified 5 2 2 Influence of methanol Methanol with oil is one of the reagents of the transesterification The amount of methanol used will lead to high variations in the results of the reaction Moreover saving methanol means lower costs when producing biodiesel Different amounts were tried to find out the best option Allthe reactions were done at room temperature 38 Amount of Reaction Vglycero Mglycero Mbiodiesel Mbiodiesel 3 27 test Sample Voi mL MkixoH 9 methanol mL time h mL e mL e 500 6 8 5 104 103 7 420 372 1 Not passed 500 6 8 5 98 100 6 465 403 9 Not passed 500 6 8 5 94 96 9 490 421 9 Passed Table 5 10 Influence of the amount of methanol in the production of biodiesel Only when 100 mL of methanol was used that is 20 of the amount of rapeseed oil the reaction was complete Furthermore with low quantities of methanol the separation of the glycerol and biodiesel phases became complicated due to the high viscosity of the glycerol The
63. el contained a lower soap and sodium con tent than the water washed and dried sam ple Again the Magnesol treated biodiesel showed a significant improvement in oxidative stability when compared to both the original methyl esters and the water washed and dried sample During his presentation Cooke con cluded that the benefits of treating methyl esters with Magensol are multi fold He reiterated Bertram s claims about the product With Magnesol there is no water effluent no emulsification improved oxidative stability minimal yield loss and minimal capital expenditure all through an application that expedites the purifica tion process and allows for continuous 43 operation Fielding questions from attendees Cooke said the cost of using Magnesol is in the range of 1 cent to 10 cents per gal lon of finished biodiesel depending on the starting contaminant level However he reminded attendees that the filter cake could potentially be used as an animal feed It has a certain nutritional value he said According to Bertram the capital costs of transitioning a biodiesel facility to Magnesol are relatively low That s because only a low tech filtering system is required In addition to potentially eliminating the drying step and the requirement for a wastewater treatment system the use of Magnesol could replace a centrifuge yield ing additional savings of capital time and maintenance costs There are less
64. eparing the standard solution that will be used for the titration The standard solution consists of 1 gram of catalyst potassium or sodium hydroxide diluted in 1 litre of water To do so 1 gram of catalyst is weighed in the balance then diluted with water This liquid is then poured in a volumetric flask and water is added till the volume is one litre 23 Once the standard solution is ready the titration itself can be performed To do so a burette filled with the standard solution has to be prepared On the other hand an Erlenmeyer flask with 10 mL of isopropyl alcohol and three drops of phenolphthalein has to be set Then it will be put on the magnetic stirrer Standard solution is added till the solution turns pink at that point the volume of standard solution is written down Next 1 mL of oil is incorporated and standard solution is added again till the solution turns pink The new volume of standard solution is noted The difference between the second and first volume is the amount of catalyst that has to be added apart from the 9 grams that are the base amount The calculations for that are as follows x mL of KOH standard solution for 1 mL of vegetable oil x L of standard solution for 1 L of vegetable oil x L of standard solution contains x g of KOH From there the amount that has to be added for the transesterification is calculated as 9 x g per litre of vegetable oil 15 4 2 Transesterification reaction The transes
65. esel Mbiodiesel Sample Type of oil Voi mL 3 27 test KOH 9 ml time h ml 9 mL 9 Linseed 6 8 500 100 5 76 81 4 495 427 4 Passed Sunflower 5 4 500 100 5 87 92 2 495 436 9 Passed Table 5 14 Results of the transesterification reaction with linseed and sunflower oils Both experiments were successful with slight differences in the amount of glycerol obtained This could be due to the differences of viscosity and properties of the oils 5 3 Soap titration Soap tests were performed for the biodiesel samples that passed the 3 27 test and were found to be significative due to different factors The result of those tests is shown in the table below As mentioned in the experimental procedure the quantity of soap in the biodiesel was calculated with the formula shown in figure 5 6 41 B 0 1 2056 E Grams of soap gram of sample A od 1000 W B mL 0 01 N HCl W g biodiesel Figure 5 6 Calculation of the grams of soap per gram of biodiesel 28 Vhcio o1 n mL Biodiesel sample g Soap biodiesel g g Room T 2 2 10 0 007 40 C 22 10 0 007 60 C 55 10 0 018 60 C 1h 4 1 10 0 013 2 3 6 2 g KOH 6 9 10 0 022 2 3 6 8 g KOH 35 10 0 018 Sunflower 3 2 10 0 010 Linseed 2 9 10 0 009 Hemp 3 8 10 0 012 Table 5 15 Soap content of different biodiesel samples The soap content varies widely depending on how the biodiesel was done that is depending on the conditions of the reaction and also on the oil used
66. esign High Capacity Rotor holds over half a litre so you can remove pounds of GUNK and clean hundreds of gallons between cleanings Modular Design Start with the basic unit and upgrade as your needs require Different videos about how is it assembled and how does it work can be found in the next links http vimeo com 8238179 http www youtube com watch v cUhgKFV5Ri4 http www youtube com watch v 5cvQazPlzKU http Awww youtube com watch v pagHQKvaC9k 2 AC Drive A GS1 AC Drive was used as a motor drive for the centrifuge In this way the rpm of the centrifuge could be maximised up to 6000 rpm and the spinning speed could also be controlled with it In the next pages the complete overview of the drive is attached GS1 Series Introduction we sam Overview The GS1 series of AC drives is our most atfordable and compact inverter offering V Hz control with general purpose appli cation features These drives can be contigured using the built in digital keypad which also allows you to set the drive speed start and stop and monitor specitic parameters or with the standard RS 485 serial communications port Standard GS1 features include one analog input four programmable digital inputs and one programmable normally open relay output Volume 13 el13 14 Drives Motors Motion GS1 Series Drives Motor Rating Hp kW 115 Volt Single Phase Input 230 Volt Three Phase Output 230 Volt S
67. essive engine gear 7 Failure of engine Collection of polyunsaturated vegetable oil lubricating oil due blow by in crankcase to the point where to polymerisation polymerisation starts Potential solution Preheat fuel prior to injection Chemically alter fuel to an ester Partially refine the oil to remove gums Filter to 4 microns Adjust injection timing Use higher compression engines Preheat fuel prior to injection Chemically alter fuel to an ester Heat fuel prior to injection Switch engine to diesel fuel when operation at part load Chemically alter the vegetable oil to an ester High viscosity of vegetable oil incomplete combustion of fuel Poor combustion at part load with vegetable oils High viscosity of vegetable oil incomplete combustion of fuel Poor combustion at part load with vegetable oils Increase motor oil changes Motor oil additives to inhibit oxidation High viscosity of vegetable oil incomplete combustion of fuel Poor combustion at part load with vegetable oils Increase motor oil changes Motor oil additives to inhibit oxidation Table 2 2 Known problems probable cause and potential solutions for using straight vegetable oil in diesels 12 2 4 Methods to improve the quality of vegetable oils Due to the many problems derived from using vegetable oils as fuels different methods have been developed to reduce their disadvantages the most important being the following a Dilution with
68. even if the production of suitable desired quality biodiesel is guaranteed it cannot be guaranteed it being economical 1 4 Method First of all familiarisation with the biodiesel producing method had to be achieved To do so different trials were carried out using different conditions and analysing the obtained results At the same time to understand the process altogether literature research was performed This apart from a better knowledge of what biodiesel is and its production implies was a good source of how to avoid mistakes and simplify the laboratory process The next step was the proper laboratory research which could be divided into three parts 1 The first of them is the production of biodiesel During this period different trials on how to produce biodiesel were performed changing reaction conditions amounts of reagents and catalysts etc 2 The second period consisted on different trials with different cleaning methods for biodiesel Both dry cleaning and water cleaning were tried In the dry cleaning four different products were tested Magnesol and D Sol both manufactured by the Dallas Group of America and two types of Aerogel manufactured by Svenska Aerogel 3 The third stage was devoted to determine the advantages of using a centrifuge in the process mainly to see its performance in the separation of two phase liquid mixtures or liquids with different kinds of impurities During the whole laboratory rese
69. eypad Setting by lt RUN gt lt STOP gt buttons Setting External Signal DI1 DI2 DI3 DI4 can be combined to offer various modes of operation RS485 communication port Outputs Multi Function Input Signal Multi step selection 0 to 3 Jog Accel decel inhibit First second accel decel switch Counter PLC operation External base block N C N O selection Multi Function Output Signal AC drive operating Frequency attained Non zero speed Base Block Fault indication Local remote indication PLC operation indication Operating Functions Automatic voltage regulation S curve Over voltage stall prevention DC braking Fault records Adjustable car ried frequency Starting frequency setting of DC braking Over current stall prevention Momentary power loss restart Reverse inhibition Frequency limits Parameter lock reset Protective Functions Overcurrent overvoltage undervoltage electronic thermal motor overload Overheating Overload Self testing Operator Interface Operator Devices 5 key 4 digit 7 segment LED 3 status LEDs potentiometer Programming Parameter values for setup and review fault codes Parameter Monitor Master Frequency Output Frequency Scaled Output Frequency Output Voltage DC Bus Voltage Output Direction Trip Event Monitor Trip History Monitor Key Functions RUN STOP DISPLAY RESET PROGRAM ENTER lt UP gt lt DOWN gt Environment E
70. f oil compared to the viscosity of mineral diesel 4 which usually leads to poor fuel atomisation incomplete combustion carbon deposition on the injector and fuel build up in the lubricant oils Moreover some other physical properties such as their lower volatility compared to mineral diesel and the reactivity of unsaturated hydrocarbon chains have led to the necessity of finding more suitable fuels 3 11 In table 2 2 a compilation of known problems when using vegetable oils as fuels as well as their probable cause and potential solution is shown Problem Probable cause Short term 1 Cold weather High viscosity low cetane and low flash point starting of vegetable oils 2 Plugging and gumming of filters lines and injectors Natural gums phosphatides in vegetable oil Other ash Very low cetane of some oils Improper 3 Engine knocking injection timing Long term 4 Coking of High viscosity of vegetable oil incomplete injectors on piston combustion of fuel Poor combustion at part and head of engine load with vegetable oils 5 Carbon deposits High viscosity of vegetable oil incomplete on piston and head combustion of fuel Poor combustion at part of engine load with vegetable oils High viscosity of vegetable oil incomplete combustion of fuel Poor combustion at part load with vegetable oils Possibly free fatty acids in vegetable oil Dilution of engine lubricating oil due to blow by of vegetable oil 6 Exc
71. f the test starts with the preparation of an Erlenmeyer flask with 100 mL of isopropyl acid and 5 drops of phenolphthalein Then ten grams of biodiesel are added If the mixture turns pink it means that there is some unreacted catalyst in the raw biodiesel In that case 0 01N HCI has to be added till the pink colour disappears In the case it doesn t that step is skipped and the next is started In the next step 18 drops of bromophenol blue are added to the mixture and then it is weighed The colour of the liquid will now be blue After this HCI which is contained in a burette is incorporated while stirring until the colour turns yellow The Erlenmeyer flask is weighed again and the volume of HCI used is noted 28 4 9 Using the centrifuge 4 9 1 Equipment The centrifuge is the most important piece of equipment needed in this part of the experimental procedure More information about it and about the AC drive can be found in the Annex VI Centrifuge AC drive Funnel Tube 4 9 2 Reagents Biodiesel Oil 32 Glycerol Water 4 9 3 Procedure The purpose of using the centrifuge was to find out whether or not it can be used for the separation of different liquids and mixtures of liquids that are often found when making biodiesel In this case the centrifuge was connected to an AC Drive allowing it to reach 6000 rpm The procedure was very simple the first step was to switch on the centrifuge and set it to the
72. hat the fuel they produce meets ASTM D 6751 specifications and other industry standards The Dallas Group broke into the North American biodiesel market with Magnesol only recently but according to one producer the adsorbent could be a cure all for most process upsets and impu rity problems that occur during biodiesel production Multiple customers nation wide in the edible oils industry are already using the product Bryan Bertram direc tor of industrial sales with The Dallas Group believes the U S biodiesel market represents one of the next big opportuni ties for the product line In an interview with Biodiesel Magazine Bertram along with Chris Abrams business development manager and Brian Cooke product devel opment specialist discussed the compa ny s ongoing efforts with Magnesol Bertram said the product increases the oxidative stability of biodiesel and is used in conjunction with or in place of the water wash treatment in the biodiesel production process After the glycerin separation process methyl esters contain contaminant materials that are detrimental to the quality of the fuel and must be eliminated from the product Reduction of the water soluble contaminants traditionally is accom plished by water washing the biodiesel However according to Bertram the era of the biodiesel water wash may be gradually ending The water wash method does nothing to remove the water insoluble What
73. he case of the cold temperature that is 30 minutes stirring 50 minutes without stiring 10 minutes stirring 50 minutes without stirring and repeating this last period until the reaction time was 5 hours The rest of the setup was 500 mL rapeseed oil 100 mL methanol 6 8 grams of KOH and the methoxide was first produced and then added to the rapeseed oil 4 2 3 6 Type of oil The reaction parameters were designed to be optimum for rapeseed oil but it had to be proven that they would work with any other kind of oil as long as the amount of free fatty acids was not too elevated To do so samples of sunflower oil and linseed oil were tested The reaction conditions were 500 mL of oil 100 mL of methanol 6 8 grams of potassium hydroxide 5 hours reaction time continuous stirring and room temperature 4 2 3 7 Acid catalyst While alkali catalysts have a higher yield and shorter reaction times they are not recommended when the content of free fatty acids in the oil is too high usually when the value obtained in the titration is higher than 3 In this cases an acid catalyst sulphuric acid with a purity of 98 is used The first part of this process is different from the process used for the alkali catalyst Initially the amount of acid has to be calculated it is done with this formula Millilitres of H2SOz per litre of oil Initial Titration Target Titration 0 2 26 Since the alkali method is recommended for titration values l
74. hings improving in terms of visual clarity Benzies says The advantage of using our systems in conjunction with Magnesol is that the towers enhance the clean up process At this point we see a rise in clarity for the first time The milkiness and cloudiness that you see in your crude methyl ester is now replaced by a bright golden crisp color After the biodiesel reaches the desired level of clarity it is transferred to a final polish tank Schoeder recom mends that all biodiesel go through a polishing step to maintain stringent quality standards irrespective of the washing method They also encourage biodiesel producers to be rigorous with their own quality testing We are the only producer of filter and purification systems that actually encourage produc ers to do these tests simply because they don t lie to you and will tell you exactly how good your purification method is Benzies says Schroeder s polishing filter units can handle from 500 liters per hour 132 gallons per hour to 2 500 liters per hour BIODIESEL Biodiesel Magazine 2008 ARTICLE WAS PRINTED IN JANUARY 2008 ISSUE OF BIODIESEL MAGAZINE January 2008 TECHNOLOGY 661 gallons per hour and remove residual particulates and water An inno vative part of the units is the built in monitoring systems that include particu late counters and water monitors The monitors display the level of contamina tion on liquid crystal displ
75. hould be met It is useless producing biodiesel in big factories using oil that has been produced in another continent and then selling the biodiesel all over the world Biodiesel is helpful when it is produced locally using seeds that are adapted to the climate of the area producing the oil next to the place where the crops are grown and if possible producing 55 the biodiesel in the same place using a simple and cheap system In this way biodiesel will be a sustainable fuel and it may even help to developing countries Finally this thesis is not complete if the issue of biodiesel versus food is not mentioned do believe that food is more important than fuels as a matter of fact human beings can live without cars but cannot live without eating However think that the issue is not so simple understand that when producing the biodiesel in an industrial way it is not sustainable and many times this can increase the price of different types of food Nevertheless since believe in the production of biodiesel in a sustainable way and locally do not think that this would affect the prices of food Mainly because farmers producing biodiesel would do so because they have soil available to grow these crops and many times the biodiesel will be for their own consumption Besides it should not be forgotten that biodiesel can be produced using waste vegetable oil which does not compete with any kind of food to be attained Therefore d
76. i method the other oils only used alkali catalyst and because of the different properties of those oils In figure 6 9 the biodiesel volumes obtained with different kinds of oils is displayed 500 375 250 125 Biodiesel volume mL 0 Ml Rapeseed Mi Linseed 7 Sunflower DB Hemp Figure 6 9 Biodiesel production from different oil sources The lower volume obtained with hemp oil may be due to the fact that acid alkali transesterification was used In the other cases the obtained biodiesel volume is almost the same 51 6 3 Soap titration Hi RoomT 40 C 60 C E 60 C th Hi 2 3 2gKOH M 2 3 6 8g KOH Sunflower DB Linseed _ Hemp 0 030 0 023 0 015 Soap biodiesel g g 0 008 Figure 6 10 Soap grams per gram of biodesel The amount of soap varies widely depending on how the biodiesel was done Both experiments that were done using the 2 3 method as well the experiments done at 60 C produce biodiesel with high soap amounts This is consistent with the observations made in the solubility tests which were much worse in those cases The reason for the difference in the production of soaps is unknown Finally it should be noted that biodiesel produced at room temperature obtains the best result in the soap titration with biodiesel produced at 40 C 6 4 Cleaning biodiesel Four different dry products were tried as well as water bubbling The best results were obtained for water bubbling and Magnesol
77. iesel where all the different methods that were tried are explained Afterwards is stated how the separation of the products and how the cleaning was done This is followed by the explanation of the different tests that were done to verify the quality of the biodiesel At last the different trials that were done with the centrifuge are described Following the experimental procedure there is a chapter that shows all the results obtained in the lab The results of all the relevant experiments performed are presented for the titration production of biodiesel cleaning soap titration and use of the centrifuge After that a discussion of the results is done stating their validity and key factors that help to understand them It is also discussed which are the best ways to produce biodiesel and the advantages and disadvantages of different methods A section about methanol an important issue when producing biodiesel is also included The last chapter are the conclusions In it the interpretation of everything that was done to obtain this thesis is conducted focusing on the key factors 2 VEGETABLE OILS AS FUELS The use of fuels whose source are vegetables is not a new discovery more than one hundred years ago Dr Rudolf Diesel used peanut oil as fuel for his engine In fact Dr Diesel designed the original diesel engine to run on vegetable oil 2 3 Vegetable oils were used in diesel engines until the 1920s However during that decade
78. iesel org index php option com_content amp view article amp id 1 53 amp ltemid 186 Access 2010 05 31 28 Make Biodiesel Soap Titration for Unwashed Biodiesel http make biodiesel org index php option com_content amp view article amp id 126 amp Itemid 157 Access 2010 05 31 58 ANNEX I PROPERTIES OF VEGETABLE OILS Fatty acid composition wt Vegetable oil 12 0 14 0 14 1 16 0 16 1 18 0 20 0 20 1 22 0 24 0 18 1 22 1 18 2 18 3 18 4 6 0 8 0 10 0 and others Cottonseed 0 28 1 0 0 0 13 0 58 0 Tobacco 0 09 10 96 0 2 3 34 14 54 69 49 0 69 0 69 Rapeseed 0 3 1 0 0 0 64 0 22 8 Safflower 0 9 2 0 0 0 12 0 78 0 Sunflower 0 6 3 0 0 0 17 0 74 0 Sesame 0 13 4 0 0 0 53 0 30 0 Lindseed 0 5 3 0 0 0 20 0 18 55 Palm tree 35 7 44 14 s E Corn 0 12 2 Tr 0 0 25 0 6 Tr Tallow 23 3 0 1 19 3 42 4 2 9 0 9 2 9 Soya bean 14 4 24 52 6 Peanut 0 11 2 1 2 1 48 0 32 1 Coconut 48 8 19 9 7 8 0 1 3 0 4 4 0 8 0 65 7 8 9 6 2 Yellow grease 0 70 0 00 14 26 1 43 8 23 0 33 0 48 43 34 26 25 2 51 0 47 Vegetable Kinematic viscosity Cetane No Heating Value Cloud Point Pour Point Flash Point Density Carbon residue oil at 38 C mm2 s C MJ kg C C C kg l wt Corn 34 9 37 6 39 5 1 1 40 277 0 9095 0 24 Cottonseed 33 5 41 8 39 5 1 7 15 234 0 9148 0 24 Crambe
79. ing heat to compare the final results of both 25 options Both 40 and 60 C were tried Apart from that the reaction was also tried at a temperature lower than room temperature approximately 2 or 3 C The factors used were 500 mL rapeseed oil 100 mL of methanol and 6 8 grams of potassium hydroxide The stirring was continuous in the case of the reactions at 40 and 60 C and the reaction time was 5 hours However due to some technical difficulties that was not possible for the low temperature trial therefore the stirring was done in the next way 30 minutes stirring 50 minutes without stirring 10 minutes stirring 50 minutes without it The last part the 10 50 was repeated until the reaction time was 5 hours As in all the previous cases the methoxide was prepared first and then it was added to the oil 4 2 3 4 Way of adding the catalyst As stated above the common method consists of preparing the methoxide before mixing it with the oil However there was not a convincing reason for this Consequently an experiment in which the methanol and the potassium hydroxide were added without being previously mixed was attempted The conditions were 500 mL rapeseed oil 100 mL methanol 6 8 grams of potassium hydroxide 6 hours reaction time room temperature and continuous stirring The methanol and the potassium hydroxide were added to the rapeseed oil at the same time without previous mixing Another way of adding the catalyst was a
80. ingle Phase Input 230 Volt Three Phase Output 230 Volt Three Phase Input Output Features e Simple Volts Hertz control e Pulse Width Modulation PWM 3 10 kHz carrier frequency IGBT technology e 130 starting torque at 5Hz e 150 rated current for one minute Electronic overload protection Stall prevention e Adjustable accel and decel ramps S curve settings for acceleration and deceleration e Manual torque boost e Automatic slip compensation DC braking e Built in EMI filter Three skip frequencies Trip history Integral keypad and speed potentiometer Programmable jog speed Three programmable preset speeds Four programmable digital inputs One programmable analog input e One programmable relay output RS 485 Modbus communications up to 19 2K e Optional Ethernet communications e UL cUL CE listed Accessories e AC line reactors RF filter Ethernet interface Four and eight port RS 485 multi drop termination board e KEPDirect O Server e GSoft drive configuration software e GS 485HD15 CBL ZIPLink RS485 Communication cable for connection to the DL06 and D2 260 15 pin ports Detailed descriptions and specifications for the accessories are available in the GS DURAPULSE Accessories section Typical Applications e Conveyors e Fans Pumps Shop tools GS1 series part numbering system GS1 2 OP5 Applicable Motor Capacity
81. ion and indeed the suitability of the biodiesel obtained from that oil depending on the climate conditions As an example palm oil is a good source for biodiesel when used in tropical countries but if it has to be used in Sweden several problems could appear because of its high cloud point In some cases when the producer of the biodiesel is also the producer of the oil the choice might be which seed to grow instead of choosing the oil type This is a very complex matter that will not be deeply analysed in this report but there are two parameters which are easy to understand and may be helpful The first of them is the production of seed per square meter that has been sown The second is the yield of oil and meal obtained by extraction of the seed In table 3 2 data for the second parameter of the major oilseeds can be seen Oilseed Oil Meal Soybean 18 3 79 5 Cottonseed 15 1 57 4 Groundnut 40 3 57 2 Sunflower 40 9 46 9 Rapeseed 38 6 60 3 Palmkernel 44 6 54 0 Copra 62 4 35 4 Linseed 33 3 64 2 Table 3 2 Yields of oil and of meal obtained by extraction of the major oilseeds 4 As shown in the table the variation on the yield of oil depending on the oilseed is significative Thus it should be considered when deciding the oilseed to use In addition other factors such as environmental conditions or geographical location should be contemplated In conclusion choosing the oil is a complex process which will be highly determined
82. is perhaps most attractive about Magnesol is that it works simply and relatively inexpensively 29 he told Biodiesel Magazine And due to the resulting effluent water it impurities gives cause for environmental concerns With Magnesol the water wash step can be eliminated and so can the liquid separation and drying of biodiesel It can also replace other methods of removing chlorophyll metals and color from biodiesel Bertram said If the processor is utilizing a costly distil lation step on the tail end to remove metals or other contaminants they could forgo that step addition a high affinity for methanol and also In Magnesol has Water so it will remove the last bits from methl esters Purification with Magnesol also the stability of biodiesel Bertram said which is becoming the demands being placed on fuel producers increases oxidative increasingly important due to by the auto manufacturing industry and government Magnesol which can be used in either March 2005 BIODIESEL MAGAZINE 40 PROCESS batch or continuous processes removes residual methanol providing a cost sav ings in the stripping step Magnesol is able to remove sulfur which is especial ly important in light of impending U S EPA regulations that will limit sulfur in diesel fuel to 15 parts per million Furthermore the product significantly reduces a plant s need for heated and conditioned wate
83. it value time weighted average TLV TWA of 10 mg m of total dust is recommended for substances for which no specific TLVs have been assigned E Magnesium silicate with an approximate chemical formula of MgO 2 6SiO is not listed in IARC Monographs on the Evaluation of the Carcinogenic Risk of Chemicals to Man 1988 Industrial Hygiene and Toxicology F A Patty Industrial Toxicology Alice Hamilton and Harriet Hardy Toxicology of the Eye W Morton Grant Dangerous Properties of Industrial Materials Sax and Lewis Government Publications a NIOSH OSHA Pocket Guide to Chemical Hazards b Registry of Toxic Effects of Chemical Substances c The Industrial Environment It s Evaluation and Control DD A DISCLAIMER OF LIABILITY The data contained herein is furnished gratuitously and independent of any sale of any product It is supplied only for your investigation and possible independent verification While the data is believed to be correct The Dallas Group of America Inc makes no representation as to the accuracy of any of the data contained herein In no event shall The Dallas Group of America Inc be responsible for any damages of any nature whatsoever directly or indirectly resulting from the publication use or reliance upon any of the data contained herein Data sheets are available for other The Dallas Group of America Inc products You are urged to obtain data sheets for all of The Dallas Group of America
84. l Top Biolabs Inc Cincinnati OH evaluated MAGNESOL products with the formula MgO 2 6SiO for acute oral toxicity albino male rat acute dermal toxicity albino rabbit skin irritation albino rabbit and eye irritation albino rabbit according to the techniques specified in the U S Federal Hazardous Substances Act The conclusions of those studies were MAGNESOL is classified as non toxic by oral administration It is not a primary skin irritant or a corrosive by dermal application It is not classified as toxic by dermal administration It is classified in Toxicity Category III corneal involvement or irritation clearing in 7 days or less by ocular administration apoy 12 ECOLOGICAL INFORMATION WATER HAZARD CLASSIFICATION Not a known pollutant This Substance does not meet PBT or vPvB criteria under Annex XIII of REACH 13 DISPOSAL CONSIDERATIONS DISPOSAL METHODS In the form supplied magnesium silicate is not classified as a hazardous waste in the U S or the EU Magnesium silicate may undergo normal non hazardous waste disposal However under RCRA it is the responsibility of the user of products to determine at the time of disposal whether the product falls under RCRA as a regulatory waste The product uses transformations synthesis mixtures etc may render the resulting end product subject to regulation See Section 10 for additional information on filter cakes 14_TRANSPORT INFORM
85. l be up to 50 C you m will need to set the carrier frequency to 2 1 kHz or Switches less and derate the output current to 80 or less See our Web site for derating curves Encoders 3 The storage temperature refers to the short term temperature during transport a 4 Conforms to the test method specified in JIS C0911 1984 Pressure Sensors Watt loss Chart a Ground braid a N copper lugs GS1 Drive Model Pushbuttons Lights GS1 10P2 l 22 FOR PAINTED SUB PANELS GS1 10P5 SCRAPE THE PAINT FROM UNDER _ Process NEATH THE STAR WASHERS GS1 20P2 Panel or single ee Relays GS1 20P5 Star washers point ground Lu GS1 21P0 Comm GS1 22P0 ee Terminal Warning AC drives generate a large Blocks amp amount of heat which may damage the Wiring AC drive Auxiliary cooling methods Air Flow are typically required in order to not Power 7 exceed maximum ambient p z l temperatures Circuit _ _ _ snoam Protection Jl lh Enclosures a Tools Il 3 Pneumatics Volume 13 www automationdirect com drives Drives Motors Motion el3 17 GS1 Specifications Terminals Main Circuit Wiring Description L1 L2 13 Input power T1 T2 13 AC drive output Ground L1 L2 L3 AUTOMATION DIRECT Control Circuit Terminals Terminal Symbol Description Relay output 1 normally open Relay output 1 common Digital input 1 Digital input 2 Digital inp
86. lso tried in this case the potassium hydroxide and the methanol were mixed to form the potassium methoxide before adding it to the oil but not all the methoxide was added at the beginning just two thirds of it The other third was added after some reaction time had taken place and the glycerol obtained had been separated This was an endeavour to see if the catalyst amount could be reduced Two different amounts of catalyst were tried 6 2 and 6 8 grams of potassium hydroxide As in the previous cases 500 mL of oil and 100 mL of methanol were used as well as continuous stirring and room temperature As explained above the methoxide was prepared and just two thirds by volume were added at the beginning After two hours the reaction was stopped and the products were poured into a separatory funnel where they stayed for half an hour enough time for the two phases to separate When the time had passed the glycerol was extracted the biodiesel was set on the stirrer again and the rest of the methoxide was added Two extra hours were necessary to complete the reaction 26 4 2 3 5 Stirring Stirring is mandatory for this reaction to start because without stirring reaction only happens in the interface which goes to a very low extent Therefore stirring is needed at least in the beginning if not during the whole reaction time To determine if continuous stirring is necessary an experiment was made using the same stirring times as in t
87. ment Pipettes Pipette bulb Test tubes 4 7 2 Reagents Raw biodiesel Water 4 7 3 Procedure Methyl esters as well as vegetable oil are not miscible with water Therefore a good quality biodiesel should have a low solubility in water which indicates that not many impurities are present To prove so a simple test was performed which consisted of mixing one volume of raw biodiesel with one volume of water in a test tube After shaking the tube it was allowed to settle for half an hour Then the extent to which biodiesel is dissolved in water the turbidity of biodiesel due to water and the amount of soap in the interface could easily be seen with a naked eye 4 8 Soap test 4 8 1 Equipment Erlenmeyer flask Pipettes Pipette bulb Burette Magnetic stirrer Balance 4 8 2 Reagents Isopropyl alcohol Phenolphthalein 0 01 N HCI 0 04 Bromophenol blue in water Biodiesel 31 4 8 3 Procedure The soap test is used to determine the amount of soap in raw biodiesel With it the quantity of dry cleaning product can be determined It is also useful to know the quality of the obtained biodiesel The grams of soap in a gram of biodiesel can be determined with the formula shown in figure 4 1 320 56 mol soap B 0 1 mol HCl Grams of soap gram of sample 1000 W B mL 001 N HCl W g biodiesel Figure 4 1 Calculation of the amount of soap in a biodiesel sample 28 The procedure o
88. nclosure Rating Protected chassis IP20 Ambient Operating Temperature 10 to 40 C 14 F to 104 F w o derating Storage Temperature 20 to 60 C 4 F to 140 F during short term transportation period Ambient Humidity 0 to 90 RH non condensing Vibration 9 8 m s2 1G less than 10Hz 5 88 m s 0 6G 20 to 50 Hz Installation Location Altitude 1000m or lower above sea level keep from corrosive gas liquid and dust Volume 13 e13 16 Drives Motors Motion Programming Software GSOFT 1 800 633 0405 GS1 Specifications Installation Understanding the installation requirements for your GS1 drive will help to ensure that it will operate within its environmental and elec trical limits NOTE Never use only this catalog for installation instructions or operation of equipment refer to the user manual GS1 M Environmental Specifications Protective Structure P20 Ambient Operating i 49 c AR M E Temperature p i Starters Storage 5 Temperatures eye Hot Humidity ON i u no condensation JU Seine Servos ati 5 9 m s 0 69 Vibration 10 to 55 Hz en Altitude 1 000 m or less m a Controls Location indoors no corrosive u gases or dust ae A ensors 1 Protective structure is based upon EN60529 A 2 2 The ambient temperature must be in the range of 10 to 40 C If the range wil
89. nd Harriet Hardy Toxicology of the Eye W Morton Grant Dangerous Properties of Industrial Materials Sax and Lewis Government Publications a NIOSH OSHA Pocket Guide to Chemical Hazards b Registry of Toxic Effects of Chemical Substances c The Industrial Environment It s Evaluation and Control Annex to Directive 67 548 EEC DNAN DISCLAIMER OF LIABILITY The data contained herein is furnished gratuitously and independent of any sale of any product It is supplied only for your investigation and possible independent verification While the data is believed to be correct The Dallas Group of America Inc makes no representation as to the accuracy of any of the data contained herein In no event shall The Dallas Group of America Inc be responsible for any damages of any nature whatsoever directly or indirectly resulting from the publication use or reliance upon any of the data contained herein Data sheets are available for other The Dallas Group of America Inc products You are urged to obtain data sheets for all of The Dallas Group of America Inc products you buy process use or distribute and you are encouraged to advise anyone working with or exposed to such products of the information contained in the applicable data sheets THE DATA IN THIS DOCUMENT IS PROVIDED WITHOUT ANY REPRESENTATION OR WARRANTY EXPRESSED OR IMPLIED REGARDING ITS ACCURACY OR CORRECTNESS NO WARRANTY EITHER EXPRESSED OR IMPLIED OF MERCHANTABILITY OR FITNESS
90. ng could only be done for half an hour at the beginning of the reaction and then for ten minutes in every hour Since the results of this experiments could not be compared with those of a reaction at room temperature with continuous stirring a trial at room temperature with the same stirring times was done The results of both tests are shown in table 5 13 Amount of Voil Vmethanc Reaction V glycerol Moiycero Vbiodiesel Mbiodiesel Sample T C 3 27 test KOH g mL mL time h mL 9 mL g 3 6 8 500 100 als 86 89 1 500 430 4 Not passed 21 room T 6 8 500 100 as 93 91 460 397 1 Passed Table 5 13 Results of the experiments at low temperature When the trial was done outside at about 3 C the reaction was not complete because the 3 27 test was not passed However the biodiesel obtained at room temperature passed the test The reaction time was longer than usual in an attempt to minimise the effect of the short stirring time It should be mentioned that the volume of biodiesel obtained in the room temperature trial was higher than 460 mL but due to some spilling part of it was lost 5 2 4 Experiments with different kinds of oils To prove the validity of the method to produce biodiesel at room temperature it was also tried using other oils apart from rapeseed oil Hemp was tried in the acid alkali method while sunflower and linseed were used with alkali catalysts Amount of Vmethano Reaction Vylycero Mglycero Vbiodi
91. nly two or one fatty acids are linked to a glycerol molecule The fatty acids present in the oils will be different from each other depending on their length and also on the number orientation and position of the double bonds 5 6 N eh O Glycerol O O nn a SE H O Figure 2 1 A triacylglycerol a diacylglycerol and a monoacylglycerol from left to right 7 8 9 2 2 Sources of oils and fats There are several types of oils and fats and they can be classified depending on their source Vegetable oils Soybeans Rapeseed Canola Safflower Barley Coconut Copra Cotton seed Groundnut Oat Rice Sorghum Wheat Winter rapeseed oil Non edible oils Animal fats Other sources Almond Lard Bacteria Abutilon muticum Tallow Algae Andiroba Poultry Fat Fungi Babassu Fish oil Micro algae Brassica carinata Tarpenes B napus Laxetes Camelina Cooking oil yellow grease Cumaru Microalgae Chroellavulgaris Cynara cadunculus Jatrophacurcas Jathropa nana Jojoba oil Pongamiaglabra Laurel Lesquerellafendleri Mahua Piqui Palm Karang Tobacco seed Rubber plant Rice bran Sesame Salmon oil Table 2 1 Classification of oils depending on their source 10 More information on different kinds of oils and their properties can be found in the Annex I 2 3 Disadvantages of vegetable oils when used as fuels However several difficulties have been found mainly concerning the high viscosity of this kind o
92. not work with the centrifuge 6 6 Methanol During the making of the thesis methanol has not been taken into account as a possible hazard in the products This is an important issue because several difficulties appear when methanol is present in any mixture Biodiesel standards set a maximum methanol amount the manufacturers of dry cleaning products recommend its removal before using their products and it has to be removed if glycerol has to be purified or if it is going to be used to produce soaps The reasons stated above show clearly how important the methanol removal is but methanol has a good property which facilitates this process it is a very volatile product so it will evaporate from biodiesel if left in contact with air Methanol spilling on soils is a serious environmental risk but its evaporation into air does not have any disadvantages 53 When doing the experimental procedure for this paper methanol was ignored in fact dry cleaning was done without removing it and it worked Actually there would probably not be too many inconveniences if using the biodiesel obtained without any methanol removal stages but it could always be left in contact with air for some time just to make sure that no problems will appear A simple test was done with biodiesel that had been left in contact with air for some time it was a mixture of different batches so the time was different for each of them the biodiesel was heated up to 120
93. ns the first of them is using excess methanol for the reaction which will mean having a completely reacted biodiesel and having to remove the methanol from both biodiesel and glycerol phases The other possible option is using lower methanol volumes which will mean a not completely reacted product and more difficulties in the separation but methanol will not have to be removed from the products The first option appears to be more suitable when standardised biodiesel is wanted and the product is going to be sold while the second is more appropriate when biodiesel for self consume is produced and it does not matter having unreacted oil in the biodiesel and not complying with the standards 6 2 4 Influence of the temperature The purpose of the different temperatures trials was to find out whether good results could be obtained at low temperatures and also find out the limits of the reaction In fact looking at the results it could be determined that the reaction does not work when the temperatures are too low 3 C lt was explained in the results section that the stirring was not continuous in that case but since the experiment was repeated with the same stirring periods but at room temperature and the reaction was complete it can be concluded that the stirring is not the determining factor Indeed the temperature is the controlling parameter There is another issue that should be carefully looked into when discussing the effects of the
94. ntially a detailed explanation in early February His presenta of how biodiesel can be purified by using the company s trademarked adsor the process the technology of filtration bent covered basic biodiesel passive and active the results of a pilot 41 BIODIESEL MAGAZINE March 2005 Biodiesel Production with a Water wash Treatment Methanol Removal Methyl Esters Catalyst NaOH Methanol Contaminated Methyl Transesterification Methyl Water Esters amp Esters Washing Residual Vegetable Water Oils used cooking oil animal fats Dirty Effluent Glycerin Biodiesel Production with Adsorbent Purification Methanol Removal Catalyst NaOH Methanol Contaminated Methyl Esters Adsorbent Purification Methyl Esters Transesterification Vegetable Oils used cooking oil animal fats Glycerin Biodiesel Purification Process Magnesol Unwashed biodiesel after separation and after methanol removal Finished Product Tank plant trial that involved the product and a brief look at replacing the water wash step with the company s magnesium silicate treatment Benefits of Cooke explained that Magnesol could treatment with be used by biodiesel producers as a total replacement of the water wash step or a MAGNESOL polishing step used to round out the water wash treatment In a standard biodiesel production v No water effluent stream proces
95. nvolved in housekeeping and spill clean up follow good industrial hygiene practices and wear proper personal protective equipment 7 HANDLING AND STORAGE USAGE PRECAUTIONS None in designated use STORAGE PRECAUTIONS None in designated use STORAGE CRITERIA No special requirements 8 EXPOSURE CONTROLS AND PERSONAL PROTECTION 8 1 Exposure Limit Values The American Conference of Government Industrial Hygienists ACGIH does not list synthetic magnesium silicate in the substance index A threshold limit value time weighted average TLV TWA of 10 mg m of total dust is recommended for substances for which no specific TLVs have been assigned In the European Union comply with all EU Member State and local guidelines 8 2 Exposure Controls No special requirements 8 3 Occupational Exposure Controls PROTECTIVE EQUIPMENT VENTILATION No special requirements RESPIRATORS If the airborne concentration exceeds the ACGIH recommended TLV an approved dust mask should be worn PROTECTIVE GLOVES Not required EYE PROTECTION Not required OTHER PROTECTION Not required HYGIENIC WORK ROUTINES No special requirements 9 PHYSICAL AND CHEMICAL PROPERTIES Normal Physical State 20 C 68 F White odorless powder pH 1 in 10 slurry 7 0 to 10 8 Melting Point 1910 C 3470 F Absolute Density H20 1 2 10 2 20 Solubility in Water Magnesium Silicate is insoluble Vapor
96. o understand the concerns of some people about biodiesel but think that if produced in a sensible way it can be helpful but of course it will not be the solution to all our problems 56 8 REFERENCES 1 Gemma Vicente Mercedes Mart nez Jos Aracil Integrated biodiesel production a comparison of different homogeneous catalysts systems Bioresource Technology 92 2004 297 305 2 E Griffin Shay Diesel fuel from vegetable oils Status and opportunities Biomass and Bioenergy 4 1993 227 242 3 Demirbas A 2008 Biodiesel A realistic fuel alternative for diesel engines London Great Britain Springer ISBN 978 1 84628 994 1 4 Gunstone F 2004 The chemistry of oils and fats Sources composition properties and uses Oxford Great Britain Blackwell Publishing Ltd ISBN 1 4051 1626 9 5 Ayhan Demirbas Fuel properties and calculation of higher heating values of vegetable oils Fuel 77 1998 1117 1120 6 X Lang A K Dalai N N Bakhshi M J Reaney P B Hertz Preparation and characterization of bio diesels from various bio oils Bioresource Technology 80 2001 53 62 7 Wikipedia Triglicerido Triglyceride http es wikipedia org wiki Triglic C3 AY9rido Access 2010 06 16 8 Wikipedia Diglyceride http en wikipedia org wiki Diglyceride Access 2010 06 16 9 Wikipedia 2 Arachidonoylglycerol http en wikipedia org wiki 2 arachidonoylglycerol Access 2010 06 16 10
97. odiesel that is going to be used by oneself or that is going to be sold As an extension to this thesis another trial to produce biodiesel is going to be done The difference between both studies is that in this new case the volumes are going to be 1000 times larger That is instead of producing batches of biodiesel of 500 mL batches of 500 litres are going to be obtained In fact this thesis is the pilot trial of the new system It is right now being constructed in the same place where this thesis took place the Faculty of Engineering and Sustainable Development but it is not finished and it has not been tried yet With this new development it will be possible to find out whether biodiesel can also be produced without any heat in large batches or if on the contrary that system only works in a lab scale In the case that as it is hoped the large scale works this method could be used by farmers to produce their own biodiesel due to its simplicity and low cost Using this system instead of a heated system means less expenditure on the equipment because it is easier to find materials It also implies less risks since the use of heat is avoided Moreover to produce biodiesel in this way does not imply a big necessity to control the system because nothing would happen if the reaction time is longer or if the raw biodiesel is left to stand for a while believe that biodiesel may help to make our world more sustainable but some conditions s
98. of alkali catalysts the most important are a slower reaction rate requirement of high reaction temperature high molar ratio of alcohol to oil separation of the catalyst serious environmental and corrosion related problems 20 12 The main advantage of the heterogeneous catalysts is that the post treatment of the products is easier because it facilitates the separation and minimises the purification In addition there is no production of soaps On the contrary it requires extreme reaction conditions and the low methyl ester yield and high reaction time are more favourable in the case of the alkali catalysed transesterification 1 Table 3 3 is a summary of the different kinds of catalysts that can be used as well as their advantages and disadvantages Type of catalyst Advantages Disadvantages Homogeneous base catalyst Heterogeneous base catalyst Homogeneous acid catalyst Heterogeneous acid catalyst Enzyme Very fast reaction rate 4000 times faster than acid catalysed transesterification Reaction can occur at mild reaction condition and less energy intensive Catalysts such as NaOH and KOH are relatively cheap and widely available Relatively faster reaction rate than acid catalysed transesterification Reaction can occur at mild reaction condition and less energy intensive Easy separation of catalyst from product High possibility to reuse and regenerate the catalyst Insensitive to FFA and water
99. on the market and industry standards have become more stringent he says US biodiesel producers are also interested in this new technology says Jonathan Dugan a product specialist with Schroeder Industries However with the current financial challenges fac ing the industry producers are being cautious with capital investments He says they talked to a couple of produc ers about developing the technology There has been some frustration with folks on the capital equipment side ask ing Why isn t anybody buying any thing Dugan says Until the govern ment puts on a tax credit or we figure out a cheaper feedstock it s a little bit of a waiting game But if crude goes up another 20 or 30 we could see a swing where biodiesel is profitable again At this time people aren t interested in retrofits They are more interested in paying for the technology they ve already purchased In addition many producers are hesitant to change from a well estab lished process Some of it has been slow going Dugan says The accept ance has been good But it has been confusing for some about how they would apply it Water washing has been the de facto standard for quite some time Adsorbent technology is new to m BIODIESEL Biodiesel Magazine 2008 ARTICLE WAS PRINTED IN JANUARY 2008 ISSUE OF BIODIESEL MAGAZINE Reprinted with permission from Biodiesel Magazine Call 701 738 4999 for reprints repu
100. onitoring technology ing point according to Benzies In our opinion producers change from wet to dry for two reasons speed and fuel qual ity he says Filtertecknik compared biodiesel produced by its system with other com mercially available fuels with surprising results Benzies says When we did pat ticle counts on standard petrodiesel it was shocking how dirty it turned out to be he says Now we are under no illu sions that it didn t leave the refinery at this cleanliness level but with so many underground storage facilities and dirty nozzles this is the cleanliness level that is being used in a lot of the motor vehi cles today Wet washed biodiesel was cleaner than the petrodiesel The dry washed biodiesel was cleaner still with a lower moisture level than the wet washed biodiesel Trends Since 2004 biodiesel producers in the United Kingdom have adopted dry wash systems That year 70 percent of producers used wet washing and 20 per cent didn t wash their biodiesel at all By PHOTO SCHROEDER INDUSTRIES 2006 43 percent of producers surveyed were dry washing their biodiesel and 47 percent were still using wet washing sys tems It wouldn t surprise me if the dry systems were to surpass the wet systems in 2007 Benzies says The reasons for this shift were because wet wash pro ducers were experiencing problems dry wash systems have now come into their own and are available
101. ons Lights Process Relays Timers Comm Terminal Blocks amp Wiring Power Circuit Protection Enclosures Tools Pneumatics Appendix Product Index Part www automationdirect com drives Drives Motors Motion Volume 13 el3 15 GS1 General Specifications General Specifications Control System Sinusoidal Pulse Width Modulation carrier frequency 3kHz 10kHz Rated Output Frequency 1 0 to 400 0 Hz limited to 9999 motor rpm Output Frequency Resolution 0 1 Hz Overload Capacity 150 of rated current for 1 minute Torque Characteristics Includes manual torque boost auto slip compensation starting torque 130 5 0Hz DC Braking Operation frequency 60 0Hz 0 30 rated voltage Start time 0 0 5 0 seconds Stop time 0 0 25 0 seconds Acceleration Deceleration Time 0 1 to 600 seconds can be set individually Voltage Frequency Pattern V F pattern adjustable Settings available for Constant Torque low and high starting torque Variable Torque low and high starting torque and user configured Stall Prevention Level Frequency li 20 to 200 or rated current Setting by lt UP gt or lt DOWN gt buttons or potentiometer Setting External Signal Potentiometer 5kO 0 5W 0 to 10 VDC input impedance 47k 3 0 to 20 mA 4 to 20 mA input impedance 2500 Multi function inputs 1 to 3 3 steps JOG UP DOWN command RS485 communication setting Operation K
102. ors have been tried with good results however using a catalyst is still necessary 17 As for microwaves they are used combined with both heterogeneous and homogeneous catalysts obtaining lower reaction times than when no microwaves are used 18 19 Depending on the type of catalyst used several advantages and disadvantages will be found The most widely used catalyst type are the alkalis and among the alkalis the most used is the potassium hydroxide This is because with this kind of catalyst the process is fast and the conditions are moderate However the disadvantage appears is the formation of soaps which are produced by neutralising the free fatty acid in the oil and triglyceride saponification Both soap formations are undesirable side reactions because they partially consume the catalyst decrease the biodiesel yield and complicate the separation and purification steps 1 Acid catalysts have not been used as widely as alkali catalysts Its main advantage is that the presence of free fatty acids will not affect the reaction Moreover acid catalysts can catalyse both esterification and transesterification at the same time The esterification is a chemical reaction in which an alcohol and an acid react producing an ester This means that the FFAs instead of producing soap as in the alkali catalysed reaction will produce esters which is the product of interest However there are some disadvantages that have induced the higher use
103. ower than three the target titration was set in that value Once the millilitres of sulphuric acid were calculated the reaction could be started As previously the acid was first mixed with the methanol and then added to the oil However there are some differences in this method because in the first part only 50 mL of methanol were added and the reaction time was approximately one day it was always left overnight Apart from that the other factors were maintained in the same way 500 mL of oil continuous stirring and room temperature were used After the first part of the reaction the liquid was poured into a separatory funnel where the water remanent was extracted Afterwards a titration was made to determine 27 whether the amount of free fatty acids was correct and then the alkali reaction was started This process was done twice with different oils old rapeseed oil and hemp oil For the hemp oil which gave the highest titration amount 100 mL of methanol were used in the alkali part On the other hand for the old rapeseed oil only 50 mL were used Besides the amount of catalyst was the obtained in the titration the reaction time was 5 hours continuous stirring was used and it was done at room temperature As in the other cases the potassium methoxide was first mixed and then it was added to the oil 15 26 4 3 Separation of the products 4 3 1Equipment The only piece of equipment which is needed for the separation of gl
104. oxide released by petroleum diesel was fixed from the atmosphere during the formative years of the earth On the other hand carbon dioxide released by biodiesel was fixed by plants in a recent year and will be recycled by the next generation of crops It has been calculated that for each kilogram of diesel not used an equivalent of 3 11 kg of CO plus an additional 15 20 for reduced processing energy is not released to the atmosphere Biodegradability Biodiesel is non toxic and degrades about four times faster than petrodiesel This is enhanced by its oxygen content higher than the oxygen content of mineral diesel Data obtained from a study shows that after 28 days biodiesel fuels were biodegraded from 77 to 89 while diesel fuel was only 18 biodegraded Table 3 5 shows biodegradability data of different fuels Fuel sample Degradation in 28 d Gasoline 91 octane 28 Heavy fuel Bunker C oil 11 Refined rapeseed oil 78 Refined soybean oil 76 Rapeseed oil methyl ester 88 Sunflower seed oil methyl ester 90 Table 3 5 Biodegradability data of petroleum and biofuels 4 Higher combustion efficiency In the literature different studies can be found supporting that esters prepared from oils can replace diesel oil Moreover it is stated that under favourable conditions biodiesel exceeds the performance of diesel fuel Improved land and water use Using biodiesel encourages using land for vegetable crops and also sensible us
105. part from that in many cases biodiesel is produced by big companies or by individuals but using complicated and expensive installations This work is an attempt to develop a way of producing biodiesel without any use of external heat using a simple procedure which could be used by people with a low knowledge of chemistry or chemical processes It also seeks to set an example on how biodiesel can be easily made by oneself without the use of any industrial systems with a low budget and limited need of supervision over the process In order to achieve that many trials were undertaken introducing changes in the different parameters that are responsible for the changes in the final product Among them changes in the amount and type of catalyst the way the catalyst is added the type of oil used the time of reaction and the temperature were made Apart from that different types of cleaning were tried starting by water cleaning and then using powder type products Magnesol D Sol and Aerogel A centrifuge was also tried to test its utility when separating impurities from liquids or different liquid phases The results of the different trials were analysed using various tests the most important being the 3 27 test the solubility test the soap titration and pH measurements To sum up it could be said that the investigation was a success since it was proved that biodiesel can be made without the use of any external heat with both alkali and acid
106. pounds had to be there Explanation for both facts can be found The glycerol was very viscous because of the evaporation of methanol which as explained previously is necessary to obtain a less viscous glycerol Methanol may have evaporated due to the high temperature Besides the mono and diglycerides seemed to dissolve in the glycerol phase which would explain the very high glycerol volumes 50 A trial with pure glycerol and raw biodiesel was done to determine the validity of this theory the results are shown in table 6 1 Temperature Reaction C Vbiodiesel mL V glycerol mL time h V glycerol mL Molycerol e Vbiodiesel mL Mbiodiesel e co o 100 5 88 106 9 380 340 1 Table 6 1 Biodiesel and pure glycerol results The volumes of both glycerol and biodiesel were lower after 5 hours this may be partly explained by the evaporation of methanol but there probably is also some dissolution of the mono and diglycerols from the biodiesel in the glycerol phase In fact glycerol that at the beginning of the experiment had no colour had certain yellow coloration when it finished 6 2 5 Experiments with different kinds of oils The fact that the transesterification reaction worked for four different kinds of oils at room temperature confirms the validity of the method The variations in biodiesel and glycerol outputs can be explained because of the use of different methods hemp oil was transesterified using the acid alkal
107. r The traditionally employed water wash method necessi tates either the purchase of centrifuges or the gravity separation of the water from biodiesel After transesterification you have methyl esters that need purification Bertram said explaining how water washing is typically used to remove con taminants from methyl esters Abrams said The Dallas Group believes the water wash method has sev eral limitations including decreased yields due to methyl ester loss in efflu ent high soap levels that cause emulsifi cation high effluent treatment and dis posal costs and the time and cost of drying methyl esters High soap levels in particular may lead to poor separation contribute to yield losses and require multiple washes to achieve specification Abrams said In some cases 24 hours are required to effect a single separation Additionally it is not uncommon for producers to end up with a methyl ester water emulsion Without a water wash there are no such emulsions formed Abrams said The disposal and even permitting of wastewater 1s difficult to impossible depending on plant location Magnesol greatly reduces dependency on water and resultant wastewater disposal issues What is perhaps most attractive about Magnesol is that it works simply and relatively inexpensively Cooke shared information about Magnesol at the 2005 National Biodiesel Conference amp Expo in Ft Lauderdale Fla tion esse
108. re is another important factor in this case the production of biodiesel It can be seen from the data that the yield of biodiesel decreases when the volume of methanol is lower 490 470 450 430 Biodiesel volume mL a 60 80 100 Methanol volume mL Figure 5 3 Variation of the volume of biodiesel produced depending on the amount of methanol A higher methanol volume in the transesterification reaction gives a higher biodiesel yield as it can be seen in figure 5 3 1 040 1 025 1 010 0 995 Glycerol density g mL 0 980 _ W SS 60 80 100 Methanol volume mL Figure 5 4 Variation of the density of glycerol depending on the volume of methanol Finally there is another important factor the density of glycerol that should not be forgotten The density is higher when higher amounts of methanol are used because the separation of the phases is better since less biodiesel is dissolved in the glycerol phase 39 5 2 3 Influence of the temperature Since the objective of this thesis is to find a suitable method to produce biodiesel without using a heat source different reactions using heat were done to compare the results of both options In this part the results of those reactions are shown Amount of Vmetnanc Reaction Voglycerol Mglycerol Vbiodiesel Mbiodiesel Sample T C Voi mL 3 27 test KOH g mL time h mL 9 mL 9 PAM CT TM 6 8 500 100 5 94 96 9 490 421 9 Passed 40 6 8 500 1
109. s Magnesol a fine white pow der is mixed with unwashed biodiesel in Y No emulsification a mixing tank for five to 10 minutes after glycerin separation and after methanol v Improved oxidative stability OSI removal E l According to Cooke magnesium sili v Minimal yield loss cate has a strong affinity for polar com e pounds thereby actively filtering out Y Minimal capital expenditure excess methanol free glycerin mono and E di glycerid d metal taminants 1 v Allows for continuous operation TOS ana mera Cona addition to free fatty acids and soap These materials are then removed from Y Expedites the purification process l the process through filtration Note v Adsorbs residual water Glycerin is a polar molecule and thereby susceptible to the adsorptive abilities of magnesium silicate Thats why Magnesol is added to the process after the glycerin separation step PROCESS Explaining the difference between passive filtration and active filtration Cooke said Magnesol has charged sites on its surface areas that attract the afore mentioned unwanted polar compounds Adsorptive sites may have either acidic or basic characteristics he said before explaining the testing methods used to measure the number and strength of adsorptive sites on a given amount of adsorbent matter such as Magnesol Cooke said testing has shown that synthetic magnesium silicate has high numbers of acidic and basi
110. t N A N A Vapor Density N A N A Volatile N A N A Evaporation Rate N A N A Ignition Temperature N A N A N A Not applicable 10 STABILITY AND REACTIVITY Stability Stable Polymerization Will not and cannot occur Conditions and Materials to Avoid None in designated use Note In sufficient quantity a filter cake composed of a flammable organic liquid absorbed on synthetic magnesium silicate or other filter materials such as diatomaceous earth Perlite or natural clays may be self heating or possibly pyrophoric o A self heating material is a material that when in contact with air and without an energy supply is liable to self heat A material of this type which exhibits spontaneous ignition or if the temperature of the sample exceeds 200 C 392 F during the 24 hour test period when tested in accordance with UN Manual of Tests and Criteria is classed as a Division 4 2 material o Apyrophoric material is a liquid or solid that even in small quantities and without an external ignition source can ignite within five 5 minutes after coming in contact with air when tested according to the UN Manual of Tests and Criteria 11 TOXICOLOGICAL INFORMATION Magnesium silicate A Albino male rat Acute oral LD50 gt 5 0 g kg B Albino rabbit Acute dermal LD50 gt 2 0 g kg Primary Irritation Index 0 80 0 No erythema skin redness 1 Very slight erythema C Albino rabbit Eyes Toxicity
111. t been evaluated as a single product The information in this section pertains mainly to Component B as Magnesium Silicate is not explosive flammable or combustible and is only a mild irritant to eyes skin and respiratory passages Inhalation Causes irritation to mucous membranes and respiratory passages Ingestion Causes irritation to the mouth and digestive tract Skin Contact Causes irritation Eye Contact Corrosive causes burns HMIS ratings scale 0 4 Magnesium silicate Component B O Health Health 0 1 Health Health 1 Fire 0 Fire 0 Reactivity 0 Reactivity 0 4 FIRST AID MEASURES D SOL 300R has not been evaluated as a single product The information in this section pertains mainly to Component B alone as Component A is only a mild irritant to eyes skin and respiratory passages Inhalation Remove to fresh air Ingestion If swallowed DO NOT INDUCE VOMITING Give large glasses of water If vomiting occurs spontaneously keep airway clear and give more water Skin Contact Flush thoroughly with cool water under shower Wash contaminated clothing and thoroughly clean shoes before reuse Eye Contact Immediately flush eyes with a directed stream of water for at least 15 minutes Remove contact lenses if worn Washing eyes within several seconds essential to achieve maximum effectiveness For all of the above GET MEDICAL ATTENTION IMMEDIATELY 5 FIRE FI
112. te magnetic stirrer 63431 410177 html Access 2010 06 16 5 Indigo Pipet Bulbs Pipetters Discontinued http www indigo com science supplies gph science supply pipet bulbs html Access 2010 06 16 6 Volumetric Aparatuses Pipette http vet kku ac th physio labbiochem 16 pipette type2 html Access 2010 06 16 7 B 4 B Performance Products http www stefs com bandb products productpages toolsccburetstand htm Access 2010 06 16 8 Carl Roth Labordedarf http www carl roth de catalogue catalogue do act showBookmark amp favOid 00000000000010c6000200238 amp lang de de amp catld DE Access 2010 06 26 9 Imalab eirl http Awww imalabeirl com catalogo vidrio3 htm Access 2010 06 26 10 Volumetric flask http commons wikimedia org wiki File Volumetric_flask_hg jpg Access 2010 06 26 11 Camlab B chner Flasks http www camlab co uk item asp itemid 36629 amp categoryid 1254 amp key amp letter amp browsecategoryid 307 Access 2010 06 26 12 Buchner funnel http commons wikimedia org wiki File Buchner_funnel jpg Access 2010 06 26 13 Hangzhou Special Paper Industry Co Ltd http special paper en made in china com product hbeEpIGVgJkO China Chemical Analysis Filter Paper html Access 2010 06 26 14 Labolan Water Jet Vacuum Pump http www labolan es detalles producto php idarea 18 amp p 1547 amp lang en Access 2010 06 26 ANNEX IV AIR FLOW MACHINE For the production of air bubbles in the wa
113. temperature It is the production of glycerol and the biodiesel production which is related to it which varies highly with the temperature reaction Figure 6 7 shows the different glycerol volumes which were obtained at different temperatures The amount of methanol is higher when the reaction temperature is increasing Moreover the volume obtained at 60 C seems to be too high 49 140 105 70 35 Glycerol volume mL 3 21 room T 40 60 Temperature C Figure 6 7 Influence of the temperature on the glycerol volume One of the options that was considered to be a reason that could explain the high glycerol volumes was the reaction time The reaction times found in the literature when temperatures around 60 C were used was usually an hour or lower In this case however the reaction time used was five hours Therefore the reaction was done at 60 C for one hour and a much lower volume of glycerol was obtained as shown in figure 6 8 140 105 70 35 Glycerol volume mL 0 Mi 60 C 5 hours 60 C 1 hour Figure 6 8 Glycerol volumes after 1 hour and 5 hours reacting at 60 C Since the reaction was complete in both cases the long reaction time seemed to be an explanation However there were another two issues that had to be explained yet on the one hand the glycerol obtained at 60 C is much more viscous than usual and the glycerol volume seemed to be too high to be just glycerol some other com
114. ter cleaning part an air flow machine is needed For this thesis a SuperFish AirFlow 4 was used its main characteristics are 4 outputs to connect to airstones filters etc Air flow rate of 10 L min Adjustable air flow Low power usage of 10 watts Low noise ANNEX V DRY CLEANING PRODUCTS 1 Magnesol Magnesol is a synthetic magnesium silicate adsorbent which is used as an adsorbent filter aid It ensures biodiesel quality by removed contaminants that can be found within the methyl esters It is manufactured by The Dallas Group of America It is composed by magnesium silicate in a 97 Different articles and the material safety data sheet for Magnesol can be found in the next pages 2 D Sol As well as Magnesol D Sol is manufactured by The Dallas Group of America it is used in the same way as Magnesol the main difference between them is their composition Magnesol is composed by magnesium silicate 97 minimum while D Sol is composed ina 70 by magnesium silicate and the rest 30 is a component B which is secret In the next pages the material safety data for D Sol and more information about it can be found 3 Aerogel svenska Aerogel AB has developed an aerogel like silicate material which has the potential to be used as a generic adsorbent The route for making the aerogel like adsorbent involves the precipitation of silica using alkali silicates and certain bi and trivalent metal ions In many respects th
115. terification reaction is the most important stage when producing biodiesel Several different experiments were tried to find the most suitable procedure First of all the equipment and reagents needed will be explained Afterwards a description of the process will be given 4 2 1 Equipment The following equipment is needed for the transesterification reaction Magnetic stirrer Volumetric pipette Pipette bulb Weight balance Erlenmeyer flask Graduated cylinder 4 2 2 Reagents Several different kinds of catalysts oils and alcohols can be used for the transesterification reaction however the ones used for the realisation of this paper are 24 Rapeseed sunflower linseed and hemp oils Methanol Potassium hydroxide sodium hydroxide and sulphuric acid 4 2 3 Procedure Several different procedures were tried to produce biodiesel Many differences can be found among them In the next sections all of them will be explained thoroughly 4 2 3 1 Amount and type of catalyst Since alkali catalysts are the most suitable for this reaction they were chosen to perform the transesterification However a choice between potassium and sodium hydroxide had to be done Moreover the exact amount of catalyst to be used had to be determined This is so because even if the transesterification is supposed to give the amount of catalyst needed it was found that using that quantity the reaction was incomplete To establish thos
116. tion parameters first with small batches to ensure the fully completion of the reaction Another important factor is that the production of glycerol 45 increases with the amount of catalyst Because of this the biodiesel yield may be affected Obtaining a pass in the 3 27 test meant that the objective of this thesis was fulfilled that is biodiesel can be produced at room temperature These first trials were helpful to determine important factors for the next experiment like the reaction time which was decided to be five hours the continuous stirring and of course the amount of potassium hydroxide to use 6 2 2 2 Amount of sodium hydroxide Sodium hydroxide as well as potassium hydroxide is one of the most widely used catalysts when producing biodiesel Sodium hydroxide compared to potassium hydroxide means using lower amounts of catalyst However it is more difficult to dissolve because of its shape potassium hydroxide is prepared as flakes while sodium hydroxide is prepared as lentils and it is also more expensive Therefore it was decided that potassium hydroxide would be the catalyst used for all the reactions _ E KOH Mi NaOH O O 14 0 2 5 10 5 Q 70 S 35 O E 0 6 Figure 6 2 Comparison between KOH and NaOH 6 2 2 3 Not preparing the potassium methoxide previously Since the 3 27 test was passed it can be said that there is not a necessity to prepare the methoxide previous to the transesterifi
117. tion temperature high alcohol to oil molar ratio and long reaction time are required Energy intensive Leaching of catalyst active sites may result to product contamination Very slow reaction rate even slower than acid catalysed transesterification High cost Sensitive to alcohol typically methanol can deactivate the enzyme Table 3 3 Advantages and disadvantages of different types of catalysts 20 3 2 3 Mechanism The mechanism for the transesterification is a series of consecutive reversible reactions where a triglyceride is converted stepwise to diglyceride monoglyceride and finally glycerol In each one of the steps a mole of ester is liberated They are reversible 13 reactions even though the equilibrium tends toward the products that is glycerol and the free fatty esters Depending on the type of catalyst chosen the mechanism of the reaction will vary In the case of the alkali catalysed reaction the mechanism was formulated in three steps in the first of them the anion of the alcohol will attack the carbonyl carbon atom of the triglyceride and a tetrahedral intermediate will be formed The second step implies that intermediate reacting with an alcohol to regenerate the anion of the alcohol Finally in the third step a rearrangement of the tetraheldral intermediate takes place resulting in the formation of a fatty acid ester and a diglyceride Pre step OH t ROH RO t H O O NaOR RO Na Stepl OR ROOCR
118. to be the standard amount of potassium hydroxide when doing the transesterification reaction with the sample 2 of rapeseed oil 110 0 105 0 100 0 95 0 Glycerol volume mL 90 0 4 1 6 2 6 8 1 8 1 8 Amount of KOH g Figure 5 1 Variation of the volume of glycerol produced depending on the amount of KOH The volume of glycerol produced increases highly with the amount of catalyst used 5 2 1 2 Amount of sodium hydroxide Amount of Voit mL Vmethano Reaction Vglycerol Mglycerol Vbiodiese Mbiodiesel oil Sample 3 27 test NaOH g mL time h ml 9 mL 9 500 100 5 79 80 4 485 418 8 Net passed Not 500 100 5 86 88 4 470 410 8 passed 500 100 9 90 85 9 480 AA Passed Table 5 4 Influence of the amount of sodium hydroxide in the production of biodiesel As in the previous case different amounts were tested When using sodium hydroxide as a catalyst only one of the samples passed the 3 27 test In the other cases the reaction was not complete 36 90 86 83 19 Glycerol volume mL ia 3 2 3 5 4 0 Amount of NaOH g Figure 5 2 Variation of the volume of glycerol produced depending on the amount of NaOH The higher the amount of sodium hydroxide used in the transesterification reaction the higher the volume of glycerol produced that can also mean a lower biodiesel yield 5 2 1 3 Not preparing the potassium methoxide previously To find out whether it was possible to do the transesterification
119. to make biodiesel 5 4 Cleaning biodiesel In order to try the different biodiesel cleaning options several biodiesel batches were prepared using the conditions that were found to be the best after all the experiments that had been performed before The data about those batches can be seen in table 5 16 Amount of Vmetnano Reaction Voglycerol Mglycerol Vbiodiesel Mbiodiesel Sample KOH 9 Voi mL mL time h mL 9 mL 9 3 27 test 1 6 8 500 100 5 98 100 3 480 413 2 Passed 2 6 8 500 100 5 94 96 9 490 421 9 Passed 3 6 8 500 100 5 92 96 5 490 424 2 Passed 4 6 8 500 100 5 91 95 0 485 423 2 Passed 5 6 8 500 100 5 93 96 3 480 414 3 Passed 6 6 8 500 100 5 99 101 8 460 406 3 Passed 7 6 8 500 100 5 99 101 3 460 403 9 Passed 8 6 8 500 100 5 94 96 9 480 413 9 Passed Table 5 16 Biodiesel batches for cleaning Soap titrations were done both before and after the cleaning The results are presented separately on the one hand the dry cleaning and on the other hand the water cleaning 42 Amount of Cleaning BR Biodiesel Soap titration Soap biodiesel Soap titration Soap biodiesel tem o before mL before g g after mL after g g mL reduction sys product g Magnesol 1 1 3 492 5 33 0 011 0 5 0 002 85 7 Magnesol 2 ES 492 5 59 0 018 1 8 0 006 67 3 D Sol 29 497 5 3 5 0 011 1 1 0 004 68 6 Aerogel 250 1 9 492 5 39 0 011 0 7 0 002 80 0 Aerogel CS 492 5 3 5 0 011 0 8 0 003 en Table 5 17 Dry cleaning results Magnesol 1 and 2
120. ustries says its system can produce clean biodiesel quickly and inexpensively By Jerry W Kram Pictured are before and after samples of fuel washed using Schroeder Industries Magnesol based dry wash system PHOTO SCHROEDER INDUSTRIES BIODIESEL M A G A Z I N Biodiesel Magazine 2008 ARTICLE WAS PRINTED IN JANUARY 2008 ISSUE OF BIODIESEL MAGAZINE January 2008 www BiodieselMagazine com TECHNOLOGY uality is the name of the game in biodiesel these days Filter clogging impurities made headlines in 2006 and biodiesel producers don t need adverse press in an economically demanding era With any business entrepreneurs rise to the challenge and create innovative and economical solutions to industry prob lems Purification is only one part of the production process and is one in our opinion that is too frequently over looked Michael of Filtertechnik Industry standards are says Benzies becoming increasingly stringent and to be adhered to in order to be in a position to upstream procedures need even start purifying A key step in producing quality biodiesel is washing to remove impuri ties such as excess caustic catalyst methanol soaps and free glycerin Along with filter clogging unwashed biodiesel can cause seal failures clogged fuel injectors damaged fuel pumps and other problems in diesel engines In the United States method of removing these impurities is the most common
121. ut 3 Digital input 4 Analog input Internal power supply 10 mA O 10 VDC Common 1 0 to 10 VDC 0 to 20 mA or 4 to 20 mA input represents zero to maximum output frequency Note Use twisted shielded twisted pair or shielded lead wires for the control signal wiring It is recommended all signal wiring be run in a separate steel conduit The shield wire should only be connected at the drive Do not connect shield wire on both ends Volume 13 el 3 1 8 Drives Motors Motion 1 800 633 0405 GS1 Specifications Basic Wiring Diagram Systems Overview Note Users MUST connect wiring according to the circuit diagram shown below Refer to user manual GS1 M for additional specific wiring information Programmable Note Refer to the following pages for explanations and information regarding line reactors and RF filters 13 50 13 67 Controllers Field I O Power Source 3 phase AC Motor Software 100 120V 10 N NO 11 C more amp 50 60Hz 5 GS XXXX other HMI E 102 50 60Hz 5 Soft Starters eve OOO l Motors amp Use terminals L1 and L2 for 120V or Gearbox select any two of the power terminals TR for 240V single phase models an x A Motor Grounding resistance Controls less than 0 10 Multi function output contacts prxmity 120VAC 24VDC 5A na Phot z 0 o 230VAC 2 5A Re Forward Sto ne P i k Fault Indication Limit Switches I i Encoders A Reverse Stop 1 o RJ 12
122. was some sedimentation time between both reaction stages and it was considered that four hours would be enougn It should also be mentioned that the result of the solubility test was much worse than the result obtained when preparing the potassium hydroxide previously 5 2 1 5 Two stage acid alkali reaction When the amount of free fatty acids is too high a two stage reaction is recommended First an acid catalyst is used and then an alkali catalyst This was done with two different kinds of oils one type of rapeseed oil and hemp oil The titration results for them were 16 7 and 27 3 grams of potassium hydroxide per litre of oil respectively Sample Type of oil Vu2so4 mL Vmethanol ML Reaction time h Titration result mL Hemp 3 50 23 3 0 Rapeseed 1 1 50 23 Re Table 5 8 Results of the acid catalised reactions After the reaction which was done overnight with continuous stirring and at room temperature the titration of the products was done obtaining low amounts of potassium hydroxide Therefore the alkali catalysed reaction could be done The results of the second stage are shown in table 5 9 5 Amount of l Vmethano Reaction Voglycerol Mglycerol Vbiodiesel Mbiodiesel Sample Type ofoil KOH g Voi ML mL time h mL 9 mL 9 Hemp 6 500 100 5 116 1233 462 405 2 Passed Rapeseed 1 9 500 50 5 100 100 8 410 361 3 Not passed 3 27 test Table 5 9 Results obtained in the second stage of the acid alkali catalysed r
123. wet washing Wet washing uses water as a solvent to carry away the impurities leaving the pure biodiesel behind But wet washing has disadvantages It s a time consuming step requiring many hours for the biodiesel and water to completely separate Wet washing can also leave residual traces of water in the fuel In drier areas you may have water gt restrictions Benzies says You may need some treatment if you have really hard water But the real problem comes with the high levels of soaps and emul sions that form if the wet wash isn t per formed properly You then have a risk of having a very poor separation of the fuel and the water and an extended sep aration time The final problem is the disposal of the hazardous effluent waste which is the byproduct of the wet wash It may be that you have to wash seven or elght times in order to achieve clarity Dry washing is an alternative In dry washing an adsorbent is added that attracts and combines with impurities separating them from the biodiesel Some systems use ion exchange resins as the adsorbent see Waterless Washing Machine in the May 2007 issue while others use a mineral called magnesium silicate one type of which is marketed under the name Magnesol by the Dallas Group of America Inc Recently lubri cant purification specialist Schroeder Industries became the exclusive distrib utor for a Magnesol based dry wash sys tem created by Filterte
124. when adding all the potassium methoxide at the same time and using 6 2 grams of potassium hydroxide the 3 27 test was not passed However in this case the test was passed so catalyst could be saved using this method On the other hand the result of the solubility test when the catalyst was added in two stages was unsatisfactory because it was much worse than the result obtained in other experiments Apart from that this method implies more handling than when adding all the potassium methoxide at the same time because there are two sedimentation stages instead of 47 one Since the purpose of this thesis is to find an easy way to produce biodiesel this option was dismissed However it could be used with satisfactory results and a lower catalyst consumption 6 2 2 5 Two stage acid alkali reaction Only one of the acid alkali catalysed reactions was successful This is probably because of the fact that only 50 mL of methanol was used in the second stage of the rapeseed reaction Methanol as explained previously is essential for the reaction to be complete The lack of methanol has two consequences the first being an incomplete reaction and the second a low biodiesel yield At the same time when excess methanol is used the glycerol volume obtained is higher than usual Those phenomena are shown in figures 6 5 and 6 6 the first shows the volumes of methanol and the second the volumes of methanol The data is about the products of the two
125. ycerol and biodiesel is a separatory funnel 4 3 2 Procedure The liquid product obtained from the transesterification reaction which was basically formed by glycerol and biodiesel is placed in the separatory funnel It stays there overnight around 18 hours and then the glycerol which is the heaviest product is separated because it forms the phase which stays in the bottom 4 4 Cleaning biodiesel with water bubbling 4 4 1 Equipment Separatory funnel Air flow machine more information about this can be found in the Annex IV 4 4 2 Reagents Raw biodiesel Water 4 4 3 Procedure The raw biodiesel which is obtained after the separation from the glycerol needs to be cleaned One of the possibilities to achieve the cleaning is using water and bubbling air through it This will dissolve the soap unreacted oil and other impurities which can be found in the raw biodiesel The steps to follow are not complicated Usually three different cleaning stages are done The first and the last are short about one hour and the intermediate is long more 28 than one day The water volume needed for every step is approximately the same as the biodiesel volume The process starts by putting the biodiesel in the separatory funnel then the water is added carefully Next the air bubbling is set and started It is important that the bubbles are not too big or too fast this may create an emulsion between the water and the biodiesel
126. zardous Waste because it exhibits the corrosive characteristic as defined in EPA rules at 40 CFR 8261 22 a 1 Under RCRA it is the responsibility of the user of products to determine at the time of disposal whether the product falls under RCRA as a regulatory waste See Section 10 for additional information on filter cakes 14 TRANSPORT INFORMATION DOT CLASS Not applicable DOT Hazardous Substance Not applicable DOT Marine Pollutant Not applicable UN NA NO Not Classified FREIGHT CLASSIFICATION NMFC 48210 Column 55 IMO CLASS Not Classified 15 REGULATORY INFORMATION The components of D SOL 300R are reported in the TOSCA Inventory 1986 The components of D SOL 300R are not listed in Sections 302 312 or 313 of SARA III 16_ OTHER INFORMATION APPROXIMATE CHEMICAL FORMULA Magnesium silicate MgO 2 6SiO gt Component B Trade secret References A through C and E are specific to magnesium silicate with the approximate chemical formula MgO 2 6SiO A 21 CFR Part 182 Subpart C Generally recognized as safe B Chemical Toxicology of Commercial Products Edition 4 1976 No acute toxicology recognized C NIOSH Registry of Toxic Effects of Chemical Substances Vol 2 1986 Irritation data Human skin 300 micro gram 3 days Very mild D American Conference of Government Industrial Hygienists The ACGIH does not list magnesium silicate in the substance index A threshold lim

study of factors influencing the quality and yield of biodiesel

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